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. 2019 Jun 11;24(11):2189. doi: 10.3390/molecules24112189

Table 1.

Positions of selected NIR bands (in cm−1) from GVPT2 anharmonic vibrational analysis in CH3CH2OH and CH3CH2OD at different levels of electronic theory and corresponding RMSE values.

Assignment Exp. Calculated
MP2/aVTZ + CPCM Diff. B2PLYP-GD3BJ/def2-TZVP + CPCM Diff. B2PLYP-GD3BJ/SNST + CPCM Diff. MP2/6-31G(d,p) + CPCM Diff. B2PLYP-GD3BJ/6-31G(d,p) + CPCM Diff. B3LYP-GD3BJ/6-31G(d,p) + CPCM Diff. B3LYP-GD3BJ/6-31G(d,p) Diff.
CH3CH2OH
2νOH 7099 7157 58 7125 26 7081 −18 7243 144 7134 35 7061 −38 7096 −3
νsCH2 + νOH 6520.4 6578 57.6 6513 −7.4 6536 15.6 6654 133.6 6576 55.6 6477 -43.4 6472 −48.4
2δas’CH3 + νOH 5886.1 5980 93.9 5889 2.9 5922 35.9 6111 224.9 5970 83.9 5871 −15.1 5892 5.9
2νasCH2 5765.7 5897 131.3 5790 24.3 5864 98.3 5957 191.3 5898 132.3 5797 31.3 5812 46.3
2νsCH2; 2νsCH3 + δsCH3 5665.1 5759 93.9 5681 15.9 5708 42.9 5812 146.9 5722 56.9 5611 −54.1 5768 102.9
[δwaggCH2, δsCH3] + νOH 5013.8 5026 12.2 5029 15.2 5012 −1.8 5114 100.2 5049 35.2 5040 26.2 5019 5.2
[δtwistCH2, δipCOH, δwaggCH2] + νOH 4954.2 4978 23.8 4979 24.8 4959 4.8 5003 48.8 5009 54.8 5008 53.8 5003 48.8
δipCOH + νOH 4873 4881 8 4868 −5 4877 4 4958 85 4926 53 4874 1 4883 10
δsCH3 + νas’CH3 4394.8 4448 53.2 4366 −28.8 4443 48.2 4592 197.2 4473 78.2 4424 29.2 4436 41.2
[δoopCOH, τCC] + νOH 4333.5 4395 61.5 4331 −2.5 4364 30.5 4502 168.5 4416 82.5 4353 19.5 4357 23.5
RMSE 70.0 RMSE 18.1 RMSE 40.8 RMSE 153.1 RMSE 72.2 RMSE 35.0 RMSE 44.6
CH3CH2OD
2νasCH3 5885.2 5978 92.8 5895 9.8 5921 35.8 6114 228.8 5967 81.8 5871 −14.2 5894 8.8
2νasCH2 5765.6 5917 151.4 5788 22.4 5862 96.4 6007 241.4 5896 130.4 5799 33.4 5815 49.4
2νOD 5277.1 5312 34.9 5289 11.9 5265 −12.1 5378 100.9 5306 28.9 5250 −27.1 5255 −22.1
δscissCH2 + νasCH2 4393.7 4445 51.3 4397 3.3 4439 45.3 4592 198.3 4493 99.3 4422 28.3 4424 30.3
[δsCH3, δwaggCH2] + νasCH3 4331.8 4392 60.2 4364 32.2 4364 32.2 4500 168.2 4415 83.2 4349 17.2 4355 23.2
[δrockCH2, δrockCH3] + νsCH2 4054.1 4057 2.9 4037 −17.1 4020 −34.1 4122 67.9 4036 −18.1 4068 13.9 4058 3.9
RMSE 80.6 RMSE 18.6 RMSE 50.0 RMSE 179.4 RMSE 83.3 RMSE 23.6 RMSE 27.3