The millimeter-wave spectrum and astronomical search of succinonitrile and its vibrational excited states ^★

Abstract

Context

Dinitriles with a saturated hydrocarbon skeleton and a −C≡N group at each end can have large electric dipole moments. Their formation can be related to highly reactive radicals such as CH₂CN, C₂N or CN. Thus, these saturated dinitriles are potential candidates to be observed in the ISM.

Aims

Our goal is the investigation of the rotational spectrum of one of the simplest dinitriles N≡C−CH₂−CH₂−C≡N, succinonitrile, whose actual rotational parameters are not precise enough to allow its detection in the ISM. In addition, the rotational spectra for its vibrational exicted states will be analyzed.

Methods

The rotational spectra of succinonitrile was measured in the frequency range 72−116.5 GHz using a new broadband millimeter-wave spectrometer based on radio astronomy receivers with Fast Fourier Transform backends. The identification of the vibrational excited states of succinonitrile was supported by high-level ab initio calculations on the harmonic and anharmonic force fields.

Results

A total of 459 rotational transitions with maximum values of J and K_a quantum numbers 70 and 14, respectively, were measured for the ground vibrational state of succinonitrile. The analysis allowed us to accurately determine the rotational, quartic and sextic centrifugal distortion constants. Up to eleven vibrational excited states, resulting from the four lowest frequency vibrational modes ν₁₃, ν₁₂, ν₂₄ and ν₂₃ were identified. In addition to the four fundamental modes, we observed overtones together with some combination states. The rotational parameters for the ground state were employed to unsuccessfully search for succinonitrile in the cold and warm molecular clouds Orion KL, Sgr B2(N), B1-b and TMC-1, using the spectral surveys captured by IRAM 30m at 3mm and the Yebes 40m at 1.3cm and 7mm.

Conclusions

 

1. Introduction

Among all the molecular species detected so far in the interstellar medium (ISM) or circumstellar shells ¹, around 200, the family of molecules containing a nitrile group represents a considerable fraction (approximately 15%). This group of molecules is constituted by simple molecular species like the CN radical or the CN⁻ anion, more complex structures like the alkyl nitriles CH₃CN (Solomon et al. 1971), C₂H₅CN (Johnson et al. 1977) or C₃H₇CN (Belloche et al. 2009, 2014), aromatic nitrile derivatives like c-C₆H₅CN (McGuire et al. 2018) or metal bearing species like AlNC (Ziurys et al. 2002) or FeCN (Zack et al. 2011). Despite dinitriles such as dicyanopolyynes, N≡C−(C≡C)_n−C≡N, are very stable species, only two dinitriles, the protonated cyanogen (NCCNH⁺) (Agúndez et al. 2015) and isocyanogen (CNCN) (Agúndez et al. 2018), a metastable isomer of NCCN, have been detected in the ISM. Dicyanopolyynes have been proposed to be abundant species in interstellar and circumstellar clouds (Kołos et al. 2000; Petrie et al. 2003) but their detection is hampered by the fact that they do not have permanent electric dipole moment and therefore cannot be observed through their rotational spectra.

Dinitriles consisting of a saturated hydrocarbon skeleton ended by a −C≡N group at each edge, i.e., N≡C−(CH₂)_n−C≡N, are potential candidates to be observed in the ISM since they can present large electric dipole moments and may be formed upon the reaction of abundant highly reactive radicals such as CH₂CN, C₂N or CN. Apart from circumstellar and interstellar regions, these dinitriles are also important molecules in planetary bodies where the atmospheres are nitrogen-rich (Kunde et al. 1981; Jolly et al. 2015). A prime example is Titan, whose atmosphere is composed of about 95% of N₂. The CH₄ molecule is the next most abundant species in Titan’s atmosphere, and when combined with N₂, their photochemistry leads to a rich variety of organic molecules including hydrocarbons, nitriles/dinitriles or tholins (Cernicharo et al., in preparation). The simplest molecule of this family of dinitriles, malononitrile (N≡C−CH₂−C≡N) and its isomers isocyanoacetonitrile (N≡C−CH₂−N≡C) and diisocyanomethane (C≡N−CH₂−N≡C) have been already investigated in the laboratory (Motiyenko et al. 2019, 2012) but their detection in the ISM has not been achieved so far. The next member of this group of dinitriles is succinonitrile, N≡C−CH₂−CH₂−C≡N, a promising candidate to be detected in the space due to its high dipole moment. In addition, its formation may proceed through a different mechanism than that for malononitrile and its isomers, and it could be easier to observe despite the simpler analogues have not been detected yet.

Succinonitrile has been studied in the centimeter wave range, using a high resolution Fourier transform microwave pulsedsupersonic jet spectrometer, and in the millimeter wave region up to 72 GHz, using a Stark modulation spectrometer (Jahn et al. 2014). The spectra of the ¹³C and ¹⁵N singly substituted isotopologues in natural abundance were also observed together with that of the chemically singly substituted deuterium isotopologues. The measurements for the parent isotopologue included 57 rotational transitions, nine of them with several nuclear quadrupole coupling hyperfine components resolved, with J≤18 and K_a≤6. In the final fit the rotational constants and all quartic distortion constants were well determined, but the astronomical search for succinonitrile at the radio telescopes observational frequency ranges becomes difficult only with these few rotational parameters.

The investigation of succinonitrile presented in this paper has two main aims. The first one is to provide a more accurate spectral modeling of succinonitrile to help its astronomical search by extending the measurements into the millimeter-wave region. The second one is to assign and analyze the rotational spectra in the low-lying vibrational states of succinonitrile, because a considerable proportion of the population resides in low-lying vibrational excited states. The necessary data to deal with spectral lines of these species can be obtained from detailed laboratory rotational measurements in the millimeter wave region. Consequently, in the present work new spectroscopic measurements of succinonitrile have been performed in the 72-116.5 GHz frequency range using a new broadband millimeter-wave spectrometer based on radio astronomy receivers with Fast Fourier Transform backends (Cernicharo et al. 2019b; Tanarro et al. 2018). The analysis of these data allowed to identify the rotational transitions of eleven different vibrational excited states belonging to fundamentals, overtones, and combination states of the lowfrequency vibrational modes.

2. Quantum chemical calculations

Although quantum chemical calculations for the succinonitrile molecule are available in the literature (Umar et al. 2007; Ramasami 2007), we carried out our own ab initio calculations in order to estimate the molecular parameters necessary to the analysis of the rotational spectrum. As shown by Jahn et al. (2014) the CCSD/cc-pVTZ level of theory is required to give an adequate description of the molecular geometry of succinonitrile. Hence, we optimized the succinonitrile molecular structure at the CCSD/cc-pVTZ level of theory using the Molpro 2018.1 ab initio program package (Werner et al. 2018). Two conformers, one antiperiplanar (trans) and another one synclinal (gauche) were found, with an energy difference of 321 cm⁻¹. The antiperiplanar conformation was found as the global minimum but it presents a C_2h symmetry and so it has no permanent dipole moment and no rotational spectrum. Therefore, we focused on the synclinal species, with a C₂ symmetry and a very large µ_b dipole moment of 5.6 D. For this conformer, harmonic and anharmonic frequency calculations were done to estimate the energy and the rotational constants of the individual vibrational excited states, facilitating the assignment of the experimental spectrum. These calculations were carried out at the CCSD/cc-pVTZ and MP2/cc-pVTZ levels of theory, using the Molpro 2018.1 and Gaussian16 (Frisch et al. 2016) program packages, respectively. An energy diagram for the vibrational levels below 500 cm⁻¹ is shown in Figure 1 and a complete list of the vibrational frequencies is given in Table A.1.

Fig. 1.

Diagram of harmonic vibrational energy levels for succinonitrile predicted below 500 cm⁻¹. Calculations done at the CCSD/cc-pVTZ level of theory.

3. Experimental

The emission rotational spectrum of succinonitrile was recorded from 72 to 116.5 GHz at room temperature using the GACELA (GAS CEll for Laboratory Astrophysics) spectrometer constructed at the Yebes Observatory (Spanish National Geographic Institute (IGN)). The detailed description can be found in Cernicharo et al. (2019b). The broadband high resolution rotational spectrometer is equipped with radio receivers similar to those used in radio astronomy to search for molecular emission in space. The receivers are equipped with 16 x 2.5 GHz Fast Fourier Transform Spectrometers (FFTs) with a spectral resolution of 38.14 kHz allowing the observation of the rotational transitions in the Q (31.5-50 GHz) and W bands (72-116.5 GHz). The spectrometer’s cell consists of a stainless steel cylinder of 890 mm length and 490 mm diameter, and positioned with the long axis horizontally. The cylinder is closed by 30 mm thick plates that support the flanges for the microwave windows, which are tilted by 9 degrees, one with respect to the vertical plane and the other with respect to the horizontal plane.

Succinonitrile (Sigma, purity >99%) is solid at room temperature and it was placed into a Pyrex™ vacuum Schlenk specially designed for these experiments, and degassed, using the common freeze-pump-thaw cycling method. In order to avoid sample condensation during the experiment, the temperature of the sample container and the injection line were kept at 50°C using a dry heating tape and a PID temperature controller. Prior to the sample introduction, the pressure inside the vacuum chamber was 2.0x10⁻⁴ mbar and during the experiment, carried out in continuous flow mode, the pressure was kept at 7.0x10⁻³ mbar, because higher pressures produce undesirable line broadenings. With the selected working pressure, the rotational lines of succinonitrile have a HWHM of 0.3−0.45 MHz which is well adapted to frequency measurements with high accuracy. In all these experiments frequency switching with a throw of 25 MHz was selected as the observing procedure. It has been previously confirmed as the most suitable mode since the lines are observed twice and the noise improves by a factor square root of two, allowing the derivation of accurate line profiles and intensities for lines of up to 2 MHz full width at half maximum (FWHM).

4. Rotational spectrum and analysis

Succinonitrile can adopt two different conformations in the gas phase, antiperiplanar or synclinal, but only the latter one has permanent dipole moment and thus shows rotational spectrum. This synclinal conformer (hereafter referred to as succinonitrile) is a near prolate molecule that has a C₂ symmetry axis which coincides with its molecular b axis, and thus it has only one dipole moment component. Despite of this, succinonitrile exhibits a very rich rotational spectrum which arises from a large number of vibrational states. Figure 2 illustrates the line density in a selected frequency region of almost two GHz width. Even though the spectrum was congested, the ground state assignment was straightforward as the rotational transition frequencies with low K_a values were well predicted, within a few MHz, by using the rotational and quartic centrifugal distortion constants reported by Jahn et al. (2014). First, we searched for b-type R-branch transitions with K_a≤6, which were found relatively close to the predicted frequencies, and which were then fitted using the SPFIT program (Pickett 1991) with the A-reduction of the Watson’s Hamiltonian in I^r representation (Watson 1977). The initial fit provided a set of refined experimental constants that were used for new spectral predictions that allowed in turn the identification of b-type Q-branch transitions with K_a values from 8 to 14. In the employed assignment method the measured transitions were used to improve the transition frequency predictions and search for new ones. Finally, a total of 459 rotational transitions with maximum values of J and K_a quantum numbers 70 and 14, respectively, were assigned for the ground vibrational state of succinonitrile. A list with all the measured transitions is available at CDS. The analysis rendered the experimental rotational constants listed in Table 1 together with the data from Jahn et al. (2014). Our rotational and quartic centrifugal distortion constants agree well with those reported by Jahn et al. (2014). The main difference is found in the δ_K and d₂ values and is due to the use of different Watson’s rotor reductions. In the present work, we used a Watson’s asymmetric rotor reduction while Jahn et al. used the symmetric one. With the exception of δ_K and d₂, the small discrepancies between the present rotational and quartic centrifugal distortion constants and those reported by Jahn et al. can be attributed to the fact that we have rendered five sextic centrifugal distortion constants, which affects slightly the value of the rest of the floated parameters.

Fig. 2.

(Upper) Section of the rotational spectrum of succinonitrile at room temperature showing the satellite pattern for the 30_1,30−29_0,29 and 30_0,30−29_1,29 rotational transitions. (Lower) Modeled spectrum based on the anharmonic frequency MP2/cc-pVTZ calculations. Intensities are estimated using the Boltzmann population ratio at 300 K.

Table 1. Spectroscopic constants for the ground state of succinonitrile.

Constants/Units	Present work	Previous worka
A/MHz	6918.11131(80)	6918.113885(151)
B/MHz	2376.27544(56)	2376.262803(90)
C/MHz	1896.98617(59)	1896.993520(43)
ΔJ/kHz	3.67233(99)	3.5175(10)
ΔJK/kHz	-27.79568(51)	-26.8928(82)
ΔK/kHz	70.248(11)	69.482(20)
δJ/kHz	1.264983(27)	-1.26678(57)b
δK/kHz	5.98372(48)	-74.55(18)c
ΦJ/mHz	20.71(58)
ΦKJ/Hz	-1.0343(28)
ΦK/Hz	2.948(42)
ϕJ/mHz	7.9224(40)
ϕK/Hz	0.7819(13)
σfit/kHz	23.75
Nlines	459	57
Jmin/Jmax	6/70	1/18
Ka,min/Ka,max	0/14	0/6

Notes. Numbers in parentheses represent the derived uncertainty (1 σ) of the parameter in units of the last digit.

^aPrevious constants derived by Jahn et al. (2014)

^bThis value is the d₁ quartic centrifugal distortion constant since Jahn et al. (2014) used a Watson’s S-reduced Hamiltonian.

^cThis value is the d₂ quartic centrifugal distortion constant since Jahn et al. (2014) used a Watson’s S-reduced Hamiltonian.

Succinonitrile has two equivalent ¹⁴N nuclei with a spin of I = 1, so that nuclear quadrupole coupling hyperfine splittings should be expected (Gordy & Cook 1984). Using the diagonal elements of the ¹⁴N quadrupole coupling tensor previously reported by Jahn et al. (2014) we predicted the ¹⁴N nuclear quadrupole coupling hyperfine splittings but we could not observe them, not even for high K_a transitions, since these splittings are smaller than the experimental broadening of the lines. This is supported by the fact that Jahn et al. (2014) observed these splittings only for the rotational transitions measured below 18 GHz. We also searched for the rotational transitions for ¹³C and ¹⁵N species in natural abundance of succinonitrile, using the rotational constants reported by Jahn et al. (2014). The line intensities for these isotopic species are around 1/100 and 0.4/100, respectively, of the observed intensity for the main isotopologue of succinonitrile and thus the transitions could not be distinguished from the noise level.

As mentioned before, the observed conformer of succinonitrile has a C₂ symmetry and thus the intensity of its rotational transitions are subjected to spin statistics. This is due to the geometry of the molecule, which allows an interchange of identical particles by the rotation about one of the principal axes. The C_2b operation of the C₂ symmetry point group, which corresponds to the rotation about the b axis by π radians, simultaneously exchanges the positions of two non-equivalent pairs of hydrogen (fermions with I = 1/2) and two nitrogen atoms (bosons with I = 1) in the molecule. The total wavefunction, expressed as ψ_tot =ψ_eleψ_vibψ_rotψ_ns, must be symmetric, Fermi-Dirac statistics, with respect to the C_2b operation, considering the two pairs of fermions and the bosons. The corresponding wavefunctions ψ_ele and ψ_vib for the ground electronic and vibrational states are symmetric. The parity of the rotational wavefunction ψ_rot depends on the K_a and K_c values and it is symmetric for the levels with K_a + K_c = even, while for the levels with K_a + K_c = odd it is antisymmetric. Hence, to satisfy Fermi-Dirac statistics symmetric and antisymmetric nuclear spin functions must be combined with symmetric and antisymmetric rotational wavefunctions, respectively. As shown in Bunker & Jensen (1998), the total nuclear statistics weights are (2I_H + 1)²(2I_H + 1)²(2I_N + 1)² = 144, and the nuclear statistical weight for the rotational levels with K_a+ K_c = even and odd is 78 and 66, respectively. Figure 3 shows a series of R-branch rotational transitions illustrating the influence of nuclear spin statistics on the transition intensities.

Fig. 3.

Two series of R-branch rotational transitions of the ground state of succinonitrile illustrating the influence of nuclear spin statistics on the transition intensities, which are related as 13-to-11 depending on the K_a+K_c values.

The relative intensities of all the rotational transitions for the ground state agree well with the predictions, done with the SPCAT program (Pickett 1991), considering the rotational partition function at maximum value of J = 90. The rotational, vibrational and conformational partition functions at different temperatures are listed in Table 2. In addition, the abundance fraction of the gauche conformer (X_g) at different temperatures is listed in Table 2. X_g is defined as the ratio between the population of gauche and trans conformers, X_g=n_gauche/n_trans. This value can be used to estimate the total column density of succinonitrile from the column density of the gauche conformer, as it is explained in section 5.

Table 2. Rotational, vibrational and conformational partition functions for succinonitrile together with the abundance fraction of the gauche conformer (X_g) at different temperatures.

Temperature/K	Qr	Qv	Qc	Xga
300.000	146147.3	15.4	1.20	0.20
225.000	99421.3	6.5	1.12	0.12
150.000	55436.2	2.8	1.04	0.04
75.000	19659.0	1.3	1.00	1.69 ×10−3
37.500	6945.8	1.1	1.00	2.88 ×10−6
18.750	2456.3	1.0	1.00	8.32 ×10−12
9.375	869.6	1.0	1.00	6.92 ×10−23

Notes.

^aX_g is the ratio between the population of gauche and trans conformers, X_g=n_gauche/n_trans.

The spectrum in Figure 2 shows that each ground vibrational state line of succinonitrile was accompanied by many satellite lines attributable exclusively to pure rotational transitions in vibrational excited states, since no other coupling interaction is expected for this closed shell molecule. In fact, a large number of excited vibrational states are predicted below 500 cm⁻¹, as it can be seen in Figure 1. In order to assist in the assignment of these satellite lines, the rotational spectra of the lower-energy excited states were modeled on the basis of calculated first-order vibration-rotation constants α_i that define the vibrational dependence of rotational constants B_ν= B_e - ∑_i α_i (ν_i + 1/2), where B_ν and B_e substitute all three rotational constants in a given excited state and in equilibrium, respectively, and ν_i is the vibrational quantum number. The calculations were carried out with the Gaussian16 program package at the MP2/cc-pVTZ level of theory using the optimized geometry obtained at the CCSD/ccpVTZ level. As can be seen in Figure 2, the abinitio predicted pattern of transitions for the different vibrational excited states reproduces that observed in the experimental spectrum. Hence, the predictions shown in the Figure 2 were used as a guide for the vibrational excited states assignments. Predictions using the vibration-rotation constants for structures optimized at levels of theory different from CCSD/cc-pVTZ, did not give reliable results. This is explained by a wrong estimation of the ∡CCCC dihedral angle which strongly affects the relative position of the atoms involved in the motions of each normal mode and thus determines the α_i vibration-rotation constants. As pointed out before by Jahn et al., the ∡CCCC dihedral angle is properly estimated only when CCSD/cc-pVTZ level of theory calculations are used in the optimization procedure.

Up to eleven different vibrational excited states were identified following the same bootstrap method of assignment-prediction employed for the ground state. All the assigned states resulted from the four lowest frequency vibrational modes ν₁₃(A), ν₁₂(A), ν₂₄(B) and ν₂₃(B). Only ν₁₃ is a torsion mode while the other three are CCN bending modes. Their harmonic frequencies together with the normal coordinate displacement vectors are shown in Figure 4. In addition to these four fundamental modes, we found, between the eleven identified states, the second quanta of ν₁₃ and ν₁₂ (2ν₁₃ and 2ν₁₂) and the third and fourth ones of ν₁₃ (3ν₁₃ and 4ν₁₃), together with some combination states, namely ν₁₃+ν₁₂, 2ν₁₃+ν₁₂ and ν₁₃+ν₂₄. The most intense rotational transitions were observed for ν₁₃, for which a total of 351 rotational transitions were included in the fit. The derived centrifugal distortion constants, depicted in Table 3, are very similar to those found for the ground state with the difference that Φ_JK could be determined with some accuracy while this was not the case for the ground state.

Fig. 4.

Schematic visualization of four lowest frequency normal vibrational modes of succinonitrile ν₁₃, ν₁₂, ν₂₄, and ν₂₃ obtained from ab initio calculations.

Table 3. Spectroscopic constants for the ground state and vibrationally excited states of succinonitrile.

Constants/Units	Ground State	ν13	ν12	2ν13	ν13 + ν12	ν24
A/MHz	6918.11131(80)	6987.0714(22)	6874.9947(28)	7060.6476(31)	6943.203(14)	6958.8496(72)
B/MHz	2376.27544(56)	2373.8628(12)	2386.2675(17)	2370.4265(15)	2384.1652(36)	2376.8526(18)
C/MHz	1896.98617(59)	1894.1505(11)	1901.5608(14)	1891.0205(13)	1898.6948(18)	1898.7786(18)
ΔJ/kHz	3.67233(99)	3.6617(19)	3.7191(23)	3.6781(23)	3.7132(33)	3.7020(28)
ΔJK/kHz	-27.79568(51)	-28.5334(10)	-27.5273(14)	-29.4602(15)	-28.2720(62)	-28.4086(28)
ΔK/kHz	70.248(11)	75.279(18)	67.087(21)	81.358(27)	72.61(12)	73.332(66)
δJ/kHz	1.264983(27)	1.271132(73)	1.28738(30)	1.28068(14)	1.2990(13)	1.27704(22)
δK/kHz	5.98372(48)	6.5624(22)	5.9509(25)	7.2189(33)	6.5426(65)	6.1714(38)
ΦJ/mHz	20.71(58)	13.1(10)	20.8(12)	14.0(12)	17.2(16)	19.4(15)
ΦJK/mHz	-	9.68(85)	-	4.15(16)	-	-
ΦKJ/Hz	-1.0343(28)	-1.1824(53)	-0.9278(52)	-1.4840(85)	-0.942(22)	-0.986(13)
ΦK/Hz	2.948(42)	3.628(62)	2.751(69)	4.542(88)	5.26(36)	2.50(21)
ϕJ/mHz	7.9224(40)	7.192(11)	8.580(75)	6.506(33)	10.94(54)	7.941(35)
ϕK/Hz	0.7819(13)	0.685(12)	0.6942(68)	0.827(24)	0.469(43)	0.922(15)
σrms/kHz	23.75	24.56	25.32	26.99	31.64	33.94
σwrmsb	0.79c	0.82c	0.51d	0.54d	0.63d	0.68d
Nlines	459	351	251	293	140	189
Jmin/Jmax	6/70	6/66	13/46	11/58	15/44	14/54
Ka,min/Ka,max	0/14	0/13	0/12	0/12	0/12	0/13
Constants/Units	3ν13	4ν13	2ν12	2ν13 + ν12	ν13 + ν24	ν23
A/MHz	7139.926(91)	7215.1(33)	6782.8(31)	7015.635(74)	7028.739(79)	6776.0(61)
B/MHz	2365.777(11)	2359.11(49)	2413.60(29)	2381.0733(47)	2374.0520(56)	2381.77(61)
C/MHz	1887.5285(13)	1883.697(16)	1906.0535(32)	1895.60422(87)	1895.78252(92)	1898.585(14)
ΔJ/kHz	3.698(17)	3.6657(40)	3.6885(24)	3.65579(67)	3.67139(73)	-3.6590(38)
ΔJK/kHz	-30.64(24)	-27.79568a	-20.18(40)	-29.934(74)	-30.096(85)	-27.79568a
ΔK/kHz	93.8(69)	70.248a	70.248a	105.3(17)	103.2(19)	70.248a
δJ/kHz	1.2881(85)	1.264983a	1.264983a	1.264983a	1.264983a	1.264983a
δK/kHz	7.78(28)	5.98372a	5.98372a	5.98372a	5.98372a	5.98372a
ΦJ/mHz	20.71a	20.71a	20.71a	20.71a	20.71a	20.71a
ΦJK/mHz	-	-	-	-	-	-
ΦKJ/Hz	-1.0343a	-1.0343a	-1.0343a	-1.0343a	-1.0343a	-1.0343a
ΦK/Hz	2.948a	2.948a	2.948a	2.948a	2.948a	2.948a
ϕJ/mHz	7.9224a	7.9224a	7.9224a	7.9224a	7.9224a	7.9224a
ϕK/Hz	0.7819a	0.7819a	0.7819a	0.7819a	0.7819a	0.7819a
σfit/kHz	32.10	26.36	36.62	28.38	31.68	36.15
σwrmsb	0.64d	0.53d	0.73d	0.57d	0.63d	0.72d
Nlines	53	15	22	45	52	20
Jmin/Jmax	20/29	20/30	18/30	18/30	18/30	19/30
Ka,min/Ka,max	0/3	0/1	0/2	0/3	0/3	0/1

Notes. Numbers in parentheses represent the derived uncertainty (1 σ) of the parameter in units of the last digit.

^aFixed to the ground-state value.

^bWeighted standard deviation of the fit.

^cThe uncertainty associated to the lines is 30 kHz.

^dThe uncertainty associated to the lines is 50 kHz.

As can be seen in the Figure 1, some states may be involved in mutual interactions as a result of proximity of their vibrational energy levels. This is the case of the 2ν₁₃ and ν₁₂ states, whose ab initio estimated energy difference is smaller than 20 cm⁻¹. These two states belong to the same symmetry (A) and therefore both Fermi and Coriolis interactions are allowed. However, only a few rotational transitions in limited J ranges (J>45) showed anomalous deviations of their experimental frequencies, which were in most of the cases smaller than 2 MHz. In different fits considering two-state perturbations analysis, we tried to determine Fermi and/or Coriolis interaction constants but these trials failed, probably because the number of perturbed transitions in our frequency range is not very large or because the interaction between both states is not strong enough to allow a combined analysis. In fact, each state could be analyzed separately, excluding some of the perturbed transitions and obtaining reasonable fits with 251 and 293 rotational transitions for the ν₁₂ and 2ν₁₃ states, respectively. From the list of the derived constants in Table 3, it can be seen how the perturbations between these two states induce departures of the values of their centrifugal distortion constants, with respect to those for the unperturbed ground state.

The rotational transitions of the ν₁₃+ν₁₂ and ν₂₄ states appeared in the spectrum very close and as shown in Table 3 they have very similar rotational constants. In spite of this, the assignment of each state could be achieved. Since ν₁₃+ν₁₂ and ν₂₄ states belong to different symmetries, A and B respectively, the influence of the nuclear spin statistics on the intensities of their rotational transitions will be opposite, with respect to K_a + K_c value. In this manner, the rotational transitions for ν₁₃+ν₁₂ may be affected like those for the ground state, where a ratio of approximately 13-to-11 was found for K_a + K_c = even / K_a + K_c =odd. In contrast, for ν₂₄ an inverse ratio of 11-to-13 should be observed for those values of K_a + K_c, since for ν₂₄ ψ_vib is antisymmetric and therefore the nuclear statistical weights for the rotational levels are reversed. This effect is illustrated in Figure 5. Taking this into account, the ν₁₃+ν₁₂ and ν₂₄ states were assigned and a total of 140 and 189 rotational transitions, including both Q- and R-branch transitions, were measured for each state, respectively. This assignment was supported by the fact that the experimental rotational constants for the ν₁₃+ν₁₂ state agree very well, with uncertainties of less than 1 MHz, with those estimated by the independent experimental/theoretical correction factors for the ν₁₃ and ν₁₂ states. On the other hand, although our calculations predicted that the ν₁₃+ν₁₂ and ν₂₄ states lie close in energy, no perturbations were observed in the spectrum and both states could be analyzed independently.

Fig. 5.

The 23_0,23−22_1,22 and 23_1,23−22_0,22 rotational transitions for ν₁₃+ν₁₂ and ν₂₄ states showing the effects of the vibrational state symmetry and the nuclear spin statistics on transition intensities. The intensities are related as 13-to-11 depending on the K_a+K_c values.

Following the same identification procedure reported above, we identified the third and fourth quanta of ν₁₃ and the second quantum of ν₁₂. The low intensity of the rotational transitions for these states resulted in fits containing smaller number of lines, including only R-branch transitions with K_a≤3. Hence, only the rotational constants and some of the quartic centrifugal distortion constants were determined from the analysis, where the sextic centrifugal distortion constants were kept fixed to the ground state values. The remaining observed states are ν₂₃, ν₁₃+ν₂₄ and ν₁₃+ν₁₂. The identification of ν₂₃ was trivial using its calculated first-order vibration-rotation constants. In contrast, ν₁₃+ν₂₄ and 2ν₁₃+ν₁₂ have similar rotational constants but they belong to different symmetries, so their identification was carried out using the same procedure followed to identify ν₁₃+ν₁₂ and ν₂₄ states. The rotational parameters derived for these states are summarized in Table 3.

5. Search for succinonitrile in space

Using the rotational parameters for the ground state of the observed conformer, gauche, of succinonitrile obtained in this work and the MADEX code (Cernicharo 2012) we have searched for it in space. Our frequency predictions are sufficiently reliable up to 200 GHz. We focused on two high-mass star-forming regions, Orion KL and Sagittarius (Sgr) B2, on a starless core in the Taurus Molecular Cloud (TMC-1), and in the cold dark cloud Barnard 1 (B1-b). The cold dense pre-stellar core TMC1-1 has been studied in detail through systematic observations at different wavelengths (Kaifu et al. 2004; Marcelino et al. 2007, 2009). Moreover, this source is particularly rich in carbon chains and −C≡N bearing species produced by gas phase ion-molecule reactions (see e.g. Kaifu et al. 2004). B1b is another well studied prototypical cold core which contains two extremely young protostellar objects, B1b-N and B1b-S. The detection of complex molecules towards B1b-S suggests that a very young and compact object is already warming up its most immediate surroundings and, therefore, molecules from grain mantles are evaporating (Marcelino et al. 2018; Cernicharo 2012).

First, we searched for succinonitrile using the IRAM 30m data at 3 mm of TMC-1 and B1-b sources (see e.g. Marcelino et al. 2007; Cernicharo 2012). Since only a few transitions are expected at these frequencies, we focused on a couple of unresolved doublets with energies of the upper level below 20 K: 7_7,1-7_6,0 and 7_7,0-7_6,1 at 92029 MHz and 8_7,2-7_6,1 and 8_7,1-7_6,2 at 96319 MHz. We did not detect succinonitrile above the 3σ detection limit of our data. The derived upper limits for the gauche conformer of succinonitrile column density in TMC-1 and B1-b assuming local thermodynamic equilibrium (LTE) and the assumed physical parameters are summarized in Table 4.

Table 4. Physical parameters of the considered cloud cores in the astronomical search of gauche-succinonitrile.

Source	Coordinates J2000.0	HPBWa (″)	Frequenciesb (GHz)	vLSRc (km s−1)	ΔvFWHMd (km s−1)	dsoue (″)	Trotf (K)	Ngauche,g.s.g ×1014 (cm−2)
Orion KL	α=5h35m14.5s δ=−05°22′30.0″	30-21	80-115.5	5.0	6.0	10	320	≤(0.2±0.1)
				5.0	6.0	15	100	≤(0.10±0.05)
				3.0	20	10	200	≤(0.05±0.02)
				3.0	20	15	90	≤(0.05±0.02)
Sgr B2(N)	α=17h47m20.0s δ=−28°22′19.0″	30-21	80-115.5	63	6.5	2.7	200	≤(100±50)
				73	6.5	2.7	200	≤(50±25)
				53	8	2.7	200	≤(50±25)
B1-b	α=03h33m20.0s δ=31°07′34.0″	30-21	80-115.5	6.7	0.7	60	12	≤(0.002±0.001)
TMC-1	α=04h41m41.9s δ=25°41′27.0″	30-21	80-115.5	6.0	0.7	60	10	≤(0.002±0.001)

Notes.

^aHalf power beam width.

^bRange of frequencies considered in the analysis.

^cRadial velocity with respect the Local Standard of Rest.

^dFull width at half maximum.

^eSource diameter.

^fRotational temperature.

^gColumn density for gauche-succinonitrile in the ground state.

Considering that the transitions with energies above 10 K may be hardly detected in TMC-1 and B1-b, especially in TMC-1, we also searched for succinonitrile in the Yebes 40m data of those sources at 1.3 cm and 7 mm (N. Marcelino, B. Tercero, J. Cernicharo, in preparation). Nevertheless, none of the low energy lines (T_upp<10 K) expected between 20–22 GHz and 30–50 GHz were detected.

These results are not totally unexpected since gauche conformer of succinonitrile is 321 cm⁻¹ above the most stable conformer, the trans one, and thus its abundance fraction is very small at low temperatures (see Table 2). However, we searched for this species in the Taurus Molecular Cloud (TMC-1) and in the cold dark cloud Barnard 1 (B1-b) in order to provide upper limits to its column density. In addition, succinonitrile could be preferably formed in space by chemical reactions on dust grains. Thus, we also sought succinonitrile in two prototypical high-mass star-forming regions, Orion KL and Sgr B2 using the public IRAM 30m data at 3 mm (Tercero et al. 2010; Belloche et al. 2013). As in the cold cores, we did not find succinonitrile above the detection limit in any of the surveys. To provide upper limits to the column density for the gauche conformer of succinonitrile in the ground state, we used the MADEX code to derive its synthetic spectrum in both sources. We assume LTE and the physical parameters derived by Belloche et al. (2013) and Lopez et al. (2014) for CH₃CN in Sgr B2 and CH₂CHCN in Orion KL, respectively (see Table 4). Because the vibrational and conformational partition functions are significant above 100 K we also estimated the total upper limit to succinonitrile column density, including both conformers, in these sources by N_T = (N_gauche,g.s. × Q_v × Q_c) / (X_g). We found total succinonitrile column densities of ≤3 ×10¹⁵ cm⁻² and ≤1 ×10¹⁸ cm⁻² in Orion KL and Sgr B2, respectively.

These column densities are only a factor ≤10 below those derived for CH₃CN in Orion KL (Lopez et al. 2014) and Sgr B2 (Belloche et al. 2013). This suggests that the succinonitrile column density is most likely much smaller than the derived upper limit, mostly due to the high level of line confusion in the considered surveys. Moreover, as the most stable conformer is a nonpolar species, we could not derive directly molecular column densities for the most abundant conformer of succinonitrile. This fact prevents to expand the discussion by comparing our results with the abundances of other cyanides or column density ratios between the pairs CH₃OH/(CH₂OH)₂ and CH₃CN/(CH₂CN)₂, where (CH₂CN)₂ is succinonitrile.

Our results point out that the detection of the gauche conformer would imply huge abundances of trans-succinonitrile, as high as those of CH₃CN in Orion KL and Sgr B2. Nevertheless, since −C≡N bearing species as complex as C₃H₇CN have been detected in these high-mass star forming regions (Belloche et al. 2009, 2014; Pagani et al. 2017), succinonitrile could also be a moderately abundant product of surface reactions.

It is worth noting that whereas the formation of ethylene glycol (OHCH₂CH₂OH) has been discussed as a product of surface chemical reactions of the CH₂OH radical (Garrod et al. 2008), the formation of succinonitrile has not been considered so far. Belloche et al. (2009) suggested that the formation of the larger cyanides begins with cosmic ray-induced photodissociation of a smaller grain-surface alkyl cyanide molecule or with the accretion of CH₂CN radical (which may be formed in the gas phase following the evaporation of HCN). Nevertheless, the reaction of CH₂CN + CH₂CN on grains, which would strongly depend on the mobility of the CH₂CN radical, is not considered in those models. In any case, it will not be straightforward to prove this production mechanism since the search of succinonitrile in space is limited to the gauche conformer.

6. Conclusions

The present work reports a comprehensive investigation of the rotational spectra for the ground state succinonitrile and its vibrational excited states. The millimeter-wave spectrum between 72-116.5 GHz was measured using a new broadband millimeter-wave spectrometer based on radio astronomy receivers with Fast Fourier Transform backends. From the analysis we obtained accurate rotational parameters for the ground state and eleven vibrational excited states, comprising states with multiple excitacion quanta and combination states. These new laboratory data were employed to unsuccessfully search for succinonitrile in the cold and warm molecular clouds Orion KL, Sgr B2(N), B1-b and TMC-1, using the spectral surveys captured by IRAM 30m at 3mm and the Yebes 40m at 1.3cm and 7mm.