Table 1.

Relative Gibbs free energy (ΔG, kJ/mol), relative enthalpy (ΔH, kJ/mol), and enthropy (S, cal/mol*K) values of benzo(a)pyrene (BaP) formation mechanism starting from chrysene (Chr→BaP) or benzo(a)anthracene (BaA→BaP) computed at the M06-2X/6-311++G(d,p) level of theory using a fine-tuned integration grid (99 radial shells and 974 angular points per shell), at 298.15 K and 1 atm within the harmonic oscillator rigid rotor approximation.

BaA→BaP	ΔG	ΔH	S	Chr→BaP	ΔG	ΔH	S
a	0.00	0.00	108.46	A	0.00	0.00	108.91
TSab	94.50	67.86	114.51	TSAB	92.24	64.50	114.06
b	24.76	30.63	109.44	B	21.46	26.89	109.54
c	−307.39	−359.74	113.13	C	−313.47	−364.87	114.34
TScd	−255.24	−336.50	117.34	TSCD	−257.86	−339.06	117.84
d	−389.58	−435.92	114.22	D	−377.64	−424.03	114.62
TSde	−256.98	−306.65	111.54	TSDE	−265.48	−315.72	111.53
e	−358.30	−408.32	111.27	E	−372.38	−422.91	111.31
TSef	−244.05	−294.14	111.21	TSEF	−249.81	−300.47	111.21
f	−295.00	−314.47	108.36	F	−300.71	−320.71	108.38
TSfg	−243.72	−291.55	113.02	TSFG	−248.99	−297.58	112.86
g	−387.31	−401.11	109.19	G	−390.87	−405.51	108.96
h	−631.14	−700.50	115.01	H	−639.50	−708.80	115.49
TShi	−558.99	−656.73	119.65	TSHI	−567.16	−664.70	120.25
i	−649.59	−710.62	117.95	I	−655.24	−715.79	118.78
TSij1	−527.83	−590.35	117.05	TSIJ1	−533.35	−595.99	117.10
TSij2	−529.88	−592.03	116.76	TSIJ2	−533.31	−596.02	117.05
j1	−545.54	−603.31	120.90	J1	−553.65	−611.28	121.12
j2	−553.48	−610.83	120.57	J2	−552.85	−610.59	121.03
TSj1k1	−524.89	−587.64	116.58	TSJ1K1	−526.23	−588.62	117.31
TSj2k2	−526.08	−588.47	116.87	TSJ2K2	−524.15	−586.46	117.38
k1	−764.02	−827.12	116.29	K1	−755.42	−818.33	116.88
k2	−752.55	−818.11	114.32	K2	−756.29	−820.14	116.13
TSk1P	−614.19	−678.89	115.01	TSK1P	−602.87	−668.16	114.99
TSk2P	−614.69	−679.93	114.58	TSK2P	−602.96	−668.26	114.97
P	−658.89	−694.43	110.99	P	−646.93	−683.02	110.99