Saar Brian G, Steeves Adam H, Thoman John W, Howard Daryl L, Schofield Daniel P, Kjaergaard Henrik G
Department of Chemistry, Williams College, Williamstown, Massachusetts 01267, USA.
J Phys Chem A. 2005 Jun 23;109(24):5323-31. doi: 10.1021/jp058060k.
We have recorded the vibrational absorption spectrum of 1,1,1,2-tetrafluoroethane (HFC-134a) in the fundamental and first five CH-stretching overtone regions with the use of Fourier transform infrared, dispersive long-path, intracavity laser photoacoustic, and cavity ringdown spectroscopies. We compare our measured total oscillator strengths in each region with intensities calculated using an anharmonic oscillator local mode model. We calculate intensities with 1D, 2D, and 3D Hamiltonians, including one or two CH stretches and two CH stretches with the HCH bending mode, respectively. The dipole moment function is calculated ab initio with self-consistent-field Hartree-Fock and density functional theories combined with double- and triple-zeta-quality basis sets. We find that the basis set choice affects the total intensity more than the choice of the Hamiltonian. We achieve agreement between the calculated and measured total intensities of approximately a factor of 2 or better for the fundamental and first five overtones.
我们利用傅里叶变换红外光谱、色散长程光谱、腔内激光光声光谱和腔衰荡光谱,记录了1,1,1,2 - 四氟乙烷(HFC - 134a)在基频以及前五个CH伸缩倍频区域的振动吸收光谱。我们将每个区域测量的总振子强度与使用非谐振子局部模式模型计算的强度进行比较。我们分别使用一维、二维和三维哈密顿量计算强度,其中包括一个或两个CH伸缩以及两个CH伸缩与HCH弯曲模式。偶极矩函数通过自洽场哈特里 - 福克和密度泛函理论结合双ζ和三ζ质量基组从头算得到。我们发现基组的选择对总强度的影响大于哈密顿量的选择。对于基频和前五个倍频,我们实现了计算和测量的总强度之间约为2倍或更好的一致性。