An analytical approach for computing franck-condon integrals of harmonic oscillators with arbitrary dimensions

نویسندگان

  • Jia-Lin Chang
  • Cyong-Huei Huang
  • Sue-Chang Chen
  • Tsung-Hao Yin
  • Yi-Tsung Chen
چکیده

We have developed an analytical approach for computing Franck-Condon integrals (FCIs) of harmonic oscillators (HOs) with arbitrary dimensions in which the mode-mixing Duschinsky effect is taken into account. A general formula of FCIs of HOs was obtained and was applied to study the photoelectron spectroscopy of vinyl alcohol and ovalene (C(32)H(14)). The equilibrium geometries, harmonic vibrational frequencies and normal modes of vinyl alcohol, ovalene, and their cations were computed at the B3LYP/aug-cc-pVTZ or the B3LYP/6-31G(d) level, from which Franck-Condon factors were calculated and photoelectron spectra were simulated. The adiabatic ionization energies of vinyl alcohol were also computed by extrapolating the CCSD(T) energies to the complete basis set limit with aug-cc-pVXZ (X = D, T, Q, 5). The simulated photoelectron spectra of both vinyl alcohol and ovalene are in agreement with the experiments. The computed adiabatic ionization energies of syn- and anti-vinyl alcohol are in consistent with the experiment within 0.008 eV and 0.014 eV, respectively. We show, for the first time, that the analytical approach of computing FCIs is also efficient and promising for the studies of vibronic spectra of macrosystems.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

SIMPLE DERIVATION OF FRANCK-CONDON INTEGRALS

The expressions foavibrational overlap integrals of the one-dimensional harmonic wavefunctions (centenxi about different equilibrium positions and having different frequencies) have been derived in a simple and straightforward way.

متن کامل

Calculation of Franck-Condon Factors for a Number of Band Systems of Diatomic Molecules Using Hua Potential

This work deals with the calculation of Franck-Condon factors using Hua potential function for the first time. The advantages of this function have been mentioned, and the numerical methods are used to obtain Franck-Condon factors for the following band systems: Agreement between the values of this work and those obtained from other works is quite good that verifies the reliability...

متن کامل

Franck-Condon factors based on anharmonic vibrational wave functions of polyatomic molecules.

Franck-Condon (FC) integrals of polyatomic molecules are computed on the basis of vibrational self-consistent-field (VSCF) or configuration-interaction (VCI) calculations capable of including vibrational anharmonicity to any desired extent (within certain molecular size limits). The anharmonic vibrational wave functions of the initial and final states are expanded unambiguously by harmonic osci...

متن کامل

A variational approach for calculating Franck-Condon factors including mode-mode anharmonic coupling.

We have implemented our new procedure for computing Franck-Condon factors utilizing vibrational configuration interaction based on a vibrational self-consistent field reference. Both Duschinsky rotations and anharmonic three-mode coupling are taken into account. Simulations of the first ionization band of ClO(2) and C(4)H(4)O (furan) using up to quadruple excitations in treating anharmonicity a...

متن کامل

An Analytical Technique for Solving Nonlinear Oscillators of the Motion of a Rigid Rod Rocking Bock and Tapered Beams

In this paper, a new analytical approach has been presented for solving strongly nonlinear oscillator problems. Iteration perturbation method leads us to high accurate solution. Two different high nonlinear examples are also presented to show the application and accuracy of the presented method. The results are compared with analytical methods and with the numerical solution using Runge-Kutta m...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Journal of computational chemistry

دوره 34 9  شماره 

صفحات  -

تاریخ انتشار 2013