Mode selective tunneling dynamics observed by high resolution spectroscopy of the bending fundamentals of 14NH2D and 14ND2H.
作者： Marcel Snels , Hans Hollenstein , Martin Quack
DOI: 10.1063/1.2366704
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摘要: High resolution (0.004 and 0.01 cm(-1) instrumental bandwidth) interferometric Fourier transform infrared spectra of (14)NH2D (14)ND2H were measured on a Bomem DA002 spectrometer in supersonic jet expansion at room temperature. We report the analysis bending fundamentals with term values Tv(s)=1389.9063(2) Tv(a)=1390.4953(2) for nu(4b) fundamental Tv(s)=1605.6404(7) Tv(a)=1591.0019(7) nu(4a) fundamental, Tv(s)=1233.3740(2) Tv(a)=1235.8904(2) Tv(s)=1461.7941(9) Tv(a)=1461.9918(19) fundamental. In all cases Tv(s) gives position symmetric inversion sublevel (with positive parity) Tv(a) antisymmetric negative parity). The notation is chosen by correlation degenerate nu(4) mode C(3v) molecules NH3 ND3. degeneracy lifted Cs symmetry indicates symmetric, b normal respect to plane NH2D ND2H. Assignments established certainty means ground state combination differences. About 20 molecular parameters effective S-reduced Hamiltonian could be determined accurately each particular, effect Fermi resonances 2nu(2) overtone was observed, leading an increased splitting case ND2H strongly inverted order two levels NH2D. Rotational perturbations observed are probably due Coriolis interactions 2nu(2). results important understanding isotope effects ammonia as well its selective catalysis inhibition excitation different vibrational modes, treated quantum dynamics high dimensional potential hypersurfaces this molecule.
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sci-hub.se 参考文章(54)
Hans-Heinrich Limbach, Amnon Kohen, Isotope Effects In Chemistry and Biology CRC Press. pp. 931- 953 ,(2005) , 10.1201/9781420028027
G. Pineau des Forêts, S. Tiné, M. Gerin, E. Roueff, E. Falgarone, Deuterium fractionation in dense ammonia cores Astronomy and Astrophysics. ,vol. 356, pp. 1039- 1049 ,(2000)
Guy Guelachvili, Handbook of infrared standards ,(1986)
Marjo Halonen, Lauri Halonen, Abnormal inversion splitting in NH2D: rotational analysis of the nu5 bending vibrational band system Journal of Physical Chemistry A. ,vol. 110, pp. 7554- 7559 ,(2006) , 10.1021/JP061287A
Sergei N. Yurchenko, Miguel Carvajal, Hai Lin, Jingjing Zheng, Walter Thiel, Per Jensen, Dipole moment and rovibrational intensities in the electronic ground state of NH3: bridging the gap between ab initio theory and spectroscopic experiment. Journal of Chemical Physics. ,vol. 122, pp. 104317- 104317 ,(2005) , 10.1063/1.1862620
Marcel Snels, Hans Hollenstein, Martin Quack, The NH and ND stretching fundamentals of 14ND2H Journal of Chemical Physics. ,vol. 119, pp. 7893- 7902 ,(2003) , 10.1063/1.1592506
Peter A. Kollman, Norman L. Allinger, Henry F. Iii Schaefer, Peter R. Schreiner, Johann Gasteiger, Terry W. Clark, Encyclopedia of computational chemistry ,(1998)
Jonathan P. Reid, Richard A. Loomis, Stephen R. Leone, Characterization of dynamical product-state distributions by spectral extended cross-correlation: Vibrational dynamics in the photofragmentation of NH2D and ND2H Journal of Chemical Physics. ,vol. 112, pp. 3181- 3191 ,(2000) , 10.1063/1.480902
Debora Henseler, Christian Tanner, Hans-Martin Frey, Samuel Leutwyler, Intermolecular vibrations of 1-naphthol⋅NH3 and d3-1-naphthol⋅ND3 in the S0 and S1 states Journal of Chemical Physics. ,vol. 115, pp. 4055- 4069 ,(2001) , 10.1063/1.1389308
John H Moore, Nicholas D Spencer, Encyclopedia of Chemical Physics and Physical Chemistry Physics Today. ,vol. 56, pp. 66- 67 ,(2003) , 10.1063/1.1564357