Simulation of the single-vibronic-level emission spectra of HAsO and DAsO.

نویسندگان

  • Daniel K W Mok
  • Edmond P F Lee
  • John M Dyke
چکیده

The single-vibronic-level (SVL) emission spectra of HAsO and DAsO have been simulated by electronic structure/Franck-Condon factor calculations to confirm the spectral molecular carrier and to investigate the electronic states involved. Various multi-reference (MR) methods, namely, NEVPT2 (n-electron valence state second order perturbation theory), RSPT2-F12 (explicitly correlated Rayleigh-Schrodinger second order perturbation theory), and MRCI-F12 (explicitly correlated multi-reference configuration interaction) were employed to compute the geometries and relative electronic energies for the X̃(1)A(') and Ã(1)A(″) states of HAsO. These are the highest level calculations on these states yet reported. The MRCI-F12 method gives computed T0 (adiabatic transition energy including zero-point energy correction) values, which agree well with the available experimental T0 value much better than previously computed values and values computed with other MR methods in this work. In addition, the potential energy surfaces of the X̃(1)A(') and Ã(1)A(″) states of HAsO were computed using the MRCI-F12 method. Franck-Condon factors between the two states, which include anharmonicity and Duschinsky rotation, were then computed and used to simulate the recently reported SVL emission spectra of HAsO and DAsO [R. Grimminger and D. J. Clouthier, J. Chem. Phys. 135, 184308 (2011)]. Our simulated SVL emission spectra confirm the assignments of the molecular carrier, the electronic states involved, and the vibrational structures observed in the SVL emission spectra but suggest a loss of intensity in the reported experimental spectra at the low emission energy region almost certainly due to a loss of responsivity near the cutoff region (∼800 nm) of the detector used. Computed and experimentally derived re (equilibrium) and/or r0 {the (0,0,0) vibrational level} geometries of the two states of HAsO are discussed.

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

Franck-Condon simulation of the single vibronic level emission spectra of HSiF and DSiF including anharmonicity.

Potential energy functions (PEFs) of the X (1)A(') and A (1)A(") states of HSiF have been computed using the coupled-cluster single-double plus perturbative triple excitations and complete-active-space self-consistent-field multireference internally contracted configuration interaction methods, respectively, employing augmented correlation-consistent polarized-valence quadruple-zeta basis sets....

متن کامل

Single vibronic level emission spectroscopy of the low-lying electronic states of NiI

Five low-lying (Te < 2200 cm ) electronic states of NiI have been observed using single vibronic level (SVL) emission spectroscopy, via three hitherto unobserved band systems in the range 21 150– 22 410 cm . In addition to the previously characterized XD5/2 and A P3=2 states, the X D3=2, A P1=2, and BR1=2 states have been observed for the first time. The emission spectra yield term energies and...

متن کامل

Vibration and Fluorescence Spectra of Porphyrin-Cored 2,2-Bis(methylol)-propionic Acid Dendrimers

Bis-MPA dendron-coated free-base tetraphenylporphyrin and zinc-tetraphenyl-porphyrin (TPPH(2) and TPPZn) were studied in comparison with simple porphyrins (H(2)P, ZnP) by theoretical simulation of their infrared, Raman and electronic absorption spectra, as well as fluorescense emission. Infrared and fluorescence spectra of the dendrimers were measured and interpreted along with time-resolved me...

متن کامل

Image Optimization in Single Photon Emission Computed Tomography by Hardware Modifications with Monte Carlo Simulation

Introduction: In Single Photon Emission Computed Tomography (SPECT), the projection data used for image reconstruction are distorted by several factors, including attenuation and scattering of gamma rays, collimator structure, data acquisition method, organ motion, and washout of radiopharmaceuticals. All these make reconstruction of a quantitative SPECT image very difficult. Simulation of a SP...

متن کامل

Franck-Condon simulation of the single-vibronic-level emission spectra of HPClÕDPCl and the chemiluminescence spectrum of HPCl, including anharmonicity

Restricted-spin coupled-cluster single-double plus perturbative triple excitation @RCCSD~T!# potential energy functions ~PEFs! were calculated for the X̃ A9 and à A8 states of HPCl employing the augmented correlation-consistent polarized-valence-quadruple-z ~aug-cc-pVQZ! basis set. Further geometry optimization calculations were carried out on both electronic states of HPCl at the RCCSD~T! level...

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:
  • The Journal of chemical physics

دوره 144 18  شماره 

صفحات  -

تاریخ انتشار 2016