Infrared Absorption Spectra of Jahn鈥揟eller Systems: Application to the Transition-Metal Trifluorides MnF3 and NiF3
详细信息 查看全文
- 作者：Padmabati Mondal ; Wolfgang Domcke
- 刊名：Journal of Physical Chemistry A
- 出版年：2014
- 出版时间：May 29, 2014
- 年：2014
- 卷：118
- 期：21
- 页码：3726-3734
- 全文大小：457K
- 年卷期：v.118,no.21(May 29, 2014)
- ISSN：1520-5215
文摘
The theory for the calculation of vibronic absorption spectra within a Jahn鈥揟eller (JT) active electronic state from first principles has been developed. The infrared absorption spectra of the 5E鈥?ground state, the low-lying 5E鈥?excited state of MnF3, and the 4E鈥?state of NiF3 have been computed and analyzed. Dipole moment derivatives have been determined by a linear-plus-quadratic expansion of nuclear dipole moment functions in the JT-active coordinates. Electronic transition dipole moments have been taken into account in the Condon approximation in the diabatic representation. The initial and final vibronic states have been expanded in a product of diabatic electronic states and vibrational basis functions. The effect of spin鈥搊rbit coupling on the vibronic infrared spectra of these molecules in their JT-active electronic states has been investigated, by employing the Breit鈥揚auli spin鈥搊rbit operator. The effect of temperature on the vibronic infrared spectra has also been explored. These results represent the first theoretical study of vibronic infrared spectra of JT-active states in transition metal compounds.