@article {1386,
title = {Prediction of spectroscopic constants for diatomic molecules in the ground and excited states using time-dependent density functional theory},
journal = {Journal of Computational Chemistry},
volume = {27},
number = {2},
year = {2006},
note = {ISI Document Delivery No.: 999IGTimes Cited: 3Cited Reference Count: 52},
month = {Jan},
pages = {163-173},
type = {Article},
abstract = {Spectroscopic constants of the ground and next seven low-lying excited states of diatomic molecules CO, N-2, P-2, and ScF were computed using the density functional theory SAOP/ATZP model, in conjunction with time-dependent density functional theory (TD-DFT) and a recently developed Slater type basis set, ATZP. Spectroscopic constants, including the equilibrium distances r(e), harmonic vibrational frequency omega(e), vibrational anharmonicity omega(e)x(e), rotational constant B-e, centrifugal distortion constant D-e, the vibration-rotation interaction constant alpha(e), and the vibrational zero-point energy E-n(0), were generated in an effort to establish a reliable database for electron spectroscopy. By comparison with experimental values and a similar model with an established larger Slater-type basis set, et-QZ3P-xD, it was found that this model provides reliably accurate results at reduced computational costs, for both the ground and excited states of the molecules. The over all errors of all eight lowest lying electronic states of the molecules under study using the effective basis set are r(e)(+/- 4\%), omega(e)(+/- 5\% mostly without exceeding +/- 20\%), omega(e)x(e)(+/- 5\% mostly without exceeding 20\%, much more accurate than a previous study on this constant of +/- 30\%), B-e(+/- 8\%), D-e(+/- 10\%), alpha(e)(+/- 10\%), and E-n(0)(+/- 10\%). The accuracy obtained using the ATZP basis set is very competitive to the larger et-QZ3P-xD basis set in particular in the ground electronic states. The overall errors in r(e), omega(e)x(e) and alpha(e) in the ground states were given by +/- 0.7, +/- 10.1, and +/- 8.4\%, respectively, using the efficient ATZP basis set, which is competitive to the errors of +/- 0.5, +/- 9.2, and +/- 9.1\%, respectively for those constants using the larger et-QZ3P-xD basis set. The latter basis set, however, needs approximately four times of the CPU time on the National Supercomputing Facilities (Australia). Due to the efficiency of the model (TD-DFT, SAOP and ATZP), it will be readily applied to study larger molecular systems. (c) 2005 Wiley Periodicals, Inc.},
keywords = {Density Function Theroy, diatomic molecules, DIPOLE-MOMENT, ELECTRONIC-STRUCTURE, emission, EXCITATION-ENERGIES, excited, FREQUENCIES, GAUSSIAN-BASIS SETS, ground state, INDUCED POLARIZATION FUNCTIONS, ORBITALS, POTENTIALS, SPECTRA, spectroscopic constants, STATES, SURFACES},
isbn = {0192-8651},
url = {://000234382400005},
author = {Falzon, C. T. and Chong, D. P. and Wang, F.}
}
@article {1083,
title = {Augmenting basis set for time-dependent density functional theory calculation of excitation energies: Slater-type orbitals for hydrogen to krypton},
journal = {Molecular Physics},
volume = {103},
number = {6-8},
year = {2005},
note = {ISI Document Delivery No.: 918XQTimes Cited: 23Cited Reference Count: 25},
month = {Mar-Apr},
pages = {749-761},
type = {Article},
abstract = {Attention is given to the dual nature of the time-dependent density functional theory approach for predicting excitation spectra, namely its theoretical basis in dynamic polarizability and its practical implementation in computer programs as a single configuration interaction. A procedure for generating diffuse functions to be added to standard Slater-type orbital basis sets for H to Kr is proposed and tested on ten close-shell molecules. The database for comparing the performance of standard and augmented basis sets consists of the 15 lowest transitions to valence and Rydberg-like states for each of the molecules. The results of this computational study are very encouraging. The addition of new augmenting functions improves the performance of standard basis sets significantly. For example, the new augmented TZP basis set, about the same size as the standard TZ2P set (and considerably smaller than the large QZ4P set), led to an average absolute deviation of 150 predicted excitation energies of only 0.12 eV from those obtained with the very large basis set called QZ3P-3DIFFUSE, compared to 0.83, 0.79, and 0.19 eV, for the standard TZP, TZ2P, and QZ4P sets, respectively. Similar augmenting functions for Gaussian-type orbital basis sets for H to Kr are also suggested.},
keywords = {(HYPER)POLARIZABILITIES, BEHAVIOR, EXCHANGE-CORRELATION POTENTIALS, HARTREE-FOCK ORBITALS, INDUCED POLARIZATION FUNCTIONS, LOCAL-DENSITY, POLARIZABILITIES, SHAPE CORRECTIONS, STATES},
isbn = {0026-8976},
url = {://000228583300003},
author = {Chong, D. P.}
}
@article {2812,
title = {COMPARISON OF LOCAL-DENSITY AND HARTREE-FOCK CALCULATIONS OF MOLECULAR POLARIZABILITIES AND HYPERPOLARIZABILITIES},
journal = {Journal of Chemical Physics},
volume = {98},
number = {6},
year = {1993},
note = {ISI Document Delivery No.: KU222Times Cited: 120Cited Reference Count: 74},
month = {Mar},
pages = {4753-4765},
type = {Article},
abstract = {This paper presents a comparison between density functional theory local density approximation (LDA) and Hartree-Fock approximation (HFA) calculations of dipole moments, polarizabilities, and first hyperpolarizabilities, using {\textquoteright}{\textquoteright}comparable{\textquoteright}{\textquoteright} basis sets, in order to assess the relative quality of the LDA and the HFA for calculating these properties. Specifically, calculations were done using basis sets of roughly double or triple zeta plus polarization quality, with and without added field-induced polarization (FIP) functions, for the seven small molecules H-2, N2, CO, CH4, NH3, H2O, and HF, using the HFA option in the program HONDO8 and the LDA options in the programs DMol and deMon. For the calculations without FIP functions, the results from HONDO8 HFA and deMon LDA, both of which use Gaussian basis sets, are very similar, while DMol, which uses a LDA numerical atomic orbital basis set, gives substantially better results. Adding FIP functions does much to alleviate these observed basis set artifacts and improves agreement with experiment. With FIP functions, the results from the two sets of LDA calculations (deMon and DMol) are very similar to each other, but differ markedly from the HFA results, and the LDA results are in significantly better agreement with experiment. This is particularly true for the hyperpolarizabilities. This appears to be the first detailed study of DFT calculations of molecular first hyperpolarizabilities. We note that closer attention to numerical details of the finite field calculation of beta over arrow pointing both left and right is necessary than would usually be the case with traditional ab initio methods. A proof that the Hellmann-Feynman theorem holds for Kohn-Sham calculations is included in the Appendix.},
keywords = {ATOMS, BASIS-SETS, CLOSED-SHELL, ELECTRIC POLARIZABILITIES, FINITE-FIELD CALCULATIONS, HYDROGEN-FLUORIDE, INDUCED POLARIZATION FUNCTIONS, PERTURBATION CORRELATION CORRECTIONS, RAMAN-SPECTRUM, STATIC DIPOLE POLARIZABILITIES, WATER MOLECULE},
isbn = {0021-9606},
url = {://A1993KU22200045},
author = {Guan, J. G. and Duffy, P. and Carter, J. T. and Chong, D. P. and Casida, K. C. and Casida, M. E. and Wrinn, M.}
}