VIBRATIONAL ANHARMONICITY IN ETHYLENE, METHYL FLUORIDE, AND DICHLOROMETHANE: AN EXPLORATION USING GAUSSIAN 03 NORMAN C. CRAIG, Department of Chemistry.

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VIBRATIONAL ANHARMONICITY IN ETHYLENE, METHYL FLUORIDE, AND DICHLOROMETHANE: AN EXPLORATION USING GAUSSIAN 03 NORMAN C. CRAIG, Department of Chemistry and Biochemistry, Oberlin College, Oberlin, OH 44074, USA MARK M. LAW, Department of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, U. K.. DONALD C. MCKEAN, School of Chemistry, University of Edinburgh, Edinburgh EH9 3JJ, U. K. dmckean@staffmail.ed.ac.uk

Vibrational Modes of Methylene Chloridea Symm. Species Mode Approx. Descript. Wavenumber/ cm-1 a1 n1 sym. CH2 stretch 2997.66 n2 sym. CH2 bend 1435.0 n3 sym. CCl2 stretch 712.9 n4 sym. CCl2 bend 281.5 a2 n5 CH2 twist 1153 b1 n6 asym. CH2 stretch 3055 n7 asym. CH2 bend 898.66 b2 n8 CH2 rock 1268.86 n9 asym. CCl2 stretch 759.82 a Duncan, J.L.; Nivilleni, G. D.; Tullini, F. J. Mol. Spectrosc. 1986, 118, 145.

Comparisons of QC-Calculated Anharmonic Corrections Di = wi – ni (cm-1) to Fundamental Frequencies for C2H4 Mode nobsda Ddtz+b Ddccb Dmtz+b Dmccb DCCSDc dcc w ("obs") (calc) n1 Ag 3022.0 131.4 128.7 138.0 135.8 141.2 3150.7 3139.2 n5 B1g 3083.4 136.7 134.7 134.8 136.5 143.0 3218.1 3194.6 n9 B2u 3104.9 139.7 138.2 138.4 139.1 146.2 3243.1 3223.0 n11 B3u 2988.6 189.1 169.6 10.3 -74.3 160.1 3158.2 3125.5 n2 Ag 1625.4 23.1 29.0 24.4 37.8 50.4 1654.4 1693.0 n3 Ag 1343.5 24.2 25.0 35.0 27.1 28.3 1368.5 1282.2 n4 Au 1025.6 22.5 23.3 -6.9 22.1 20.8 1048.9 1067.2 n6 B1g 1222 22.6 4.4 19.5 18.8 1244.6 1246.7 n7 B1u 948.8 14.2 15.4 -50.3 17.3 17.9 964.2 979.0 n8 B2g 939.9 15.9 17.5 1015 14.0 12.4 957.4 983.4 n10 B2u 825.9 2.5 2.4 0.5 1.1 1.3 828.3 836.4 n12 B3u 1442.5 34.1 35.4 50.6 39.4 1477.9 1479.2 a Observed frequency from D. Van Lerberghe et al., J. Mol. Spectrosc. 1972, 42, 251. b dtz+ = B3LYP/6-311++G**; mtz+ = MP2/6-311++G**; dcc = B3LYP/cc-pVTZ; mcc = MP2/cc-pVTZ. c From a CCSD(T)/cc-pVTZ calculation: Martin, J.M.L.; Lee, T.J.; Taylor, P.R.; Francois, J-P. J. Chem. Phys. 1995, 103, 2589. Mode numbers as in this reference. Green: Fermi resonance treated specifically. Red: Fermi resonance not treated. Blue: Anomaly ascribed to the absence of f functions in the 6-311++G** basis set, when used in MP2 calculations.

Anomalies in Anharmonicity Constants xrs (cm-1) in C2H4 dtz+ dcc mtz+ mcc 8 2 -5.4 -5.9 8.6 -7.1 8 3 -2.1 -2.3 -18.7 -3.2 8 4 -5.8 -6.2 47.9 -4.7 8 6 5.0 4.3 33.0 6.2 8 7 -0.7 -0.6 125.3 -0.2 8 8 1.7 1.5 465.4 3.2 7 12 -3.1 -3.5 -24.8 -4.5 7 8 11 12 -69.5 -51.6 108.8 192.3 f8888 185 181 7803 225 f1188 -179 -242 -189 f4488 131 127 407 143 f6688 25 22 140 32 Blue: ascribed to the absence of f functions. Red: Fermi resonance not treated.

Methyl Fluoride Experimental anharmonic constants exist for methyl fluoride,a but deficiencies in the G03 code for degenerate modes prevented making the intended comparison between calculations and experiment. a M.M. Law; J.L. Duncan; I.M. Mills J. Mol. Struct. 1992, 260, 323.

Conclusions The Gaussian 03 code for the option anharmonic needs substantial revision if this facility is to be generally useful. The 10-cm-1 window for recognizing resonances is too small. Molecules with degenerate modes are handled improperly. (In talk MI12, the failure to ensure use of Cartesian coordinates in the principal axis system in the vib-rot module of G03 was reported.) B3LYP and MP2 models with triple-zeta quality basis sets can give satisfactory anharmonicity corrections, BUT MP2 calculations using bases without f functions can be quite wrong. Differing anharmonicity corrections can be found for in-phase and out-of-phase stretching vibrations of C-H bonds. In such cases, different scale factors should be used when scaling harmonic QC force fields to reproduce observed spectra. For 1,1-difluorocyclopropane, the G03-based anharmonic analysis of combination tones was correct for the d0 and d4 species of C2v symmetry but incorrect for the d2 species of Cs symmetry.