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Title: Spectral shift of sodium in a liquid-helium environment: A sequential Monte Carlo time-dependent density-functional-theory study

Abstract

The excitation lineshift and linewidth of the principal resonance line of Na embedded in liquid He have been obtained using combined Monte Carlo (MC) simulation and quantum mechanics (QM) calculations. The metropolis MC simulation used interatomic potentials obtained from high-level quantum mechanics results. Using the structures of the simulation statistically relevant configurations are sampled for subsequent QM calculations. The transition wavelengths for the 3s{yields}3p principal resonance line of atomic Na were obtained using time-dependent density-functional-theory calculations of the central alkali-metal atom surrounded by the first solvation shell composed of 42 He atoms. The widths are obtained by the statistical distribution of calculated transitions. Three different functionals were used. Statistically converged results using the PBE1PBE/6-311++G(d,p) give a blueshift of 14.7 nm and a width at half maximum of 7.8 nm. Similar results are obtained using the Beeke-Lee-Yang-Parr three parameter exchange functional and the Becke three-parameter exchange with the Perdew nonlocal correlation functional models. These results seem to give a reasonable statistical representation of the structure of the He cavity enclosing the host Na atom and the consequent solvent effect on the 3s{yields}3p excitation.

Authors:
; ; ;  [1];  [2];  [3]
  1. Instituto de Fisica, Universidade de SaoPaulo, CP 66318, 05315-970 Sao Paulo, SP (Brazil)
  2. (India)
  3. (Brazil)
Publication Date:
OSTI Identifier:
20786313
Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Review. A; Journal Volume: 72; Journal Issue: 6; Other Information: DOI: 10.1103/PhysRevA.72.062714; (c) 2005 The American Physical Society; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; ATOMS; COMPUTERIZED SIMULATION; CORRELATIONS; DENSITY FUNCTIONAL METHOD; DISTRIBUTION; EXCITATION; EXCITED STATES; FUNCTIONAL MODELS; FUNCTIONALS; HELIUM; LIQUIDS; MONTE CARLO METHOD; POTENTIAL ENERGY; POTENTIALS; QUANTUM MECHANICS; RESONANCE; SODIUM; SOLVENTS; SPECTRAL SHIFT; TIME DEPENDENCE

Citation Formats

Ludwig, Valdemir, Mukherjee, Prasanta K., Coutinho, Kaline, Canuto, Sylvio, Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, and Instituto de Fisica, Universidade de SaoPaulo, CP 66318, 05315-970 Sao Paulo, SP. Spectral shift of sodium in a liquid-helium environment: A sequential Monte Carlo time-dependent density-functional-theory study. United States: N. p., 2005. Web. doi:10.1103/PHYSREVA.72.0.
Ludwig, Valdemir, Mukherjee, Prasanta K., Coutinho, Kaline, Canuto, Sylvio, Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, & Instituto de Fisica, Universidade de SaoPaulo, CP 66318, 05315-970 Sao Paulo, SP. Spectral shift of sodium in a liquid-helium environment: A sequential Monte Carlo time-dependent density-functional-theory study. United States. doi:10.1103/PHYSREVA.72.0.
Ludwig, Valdemir, Mukherjee, Prasanta K., Coutinho, Kaline, Canuto, Sylvio, Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, and Instituto de Fisica, Universidade de SaoPaulo, CP 66318, 05315-970 Sao Paulo, SP. Thu . "Spectral shift of sodium in a liquid-helium environment: A sequential Monte Carlo time-dependent density-functional-theory study". United States. doi:10.1103/PHYSREVA.72.0.
@article{osti_20786313,
title = {Spectral shift of sodium in a liquid-helium environment: A sequential Monte Carlo time-dependent density-functional-theory study},
author = {Ludwig, Valdemir and Mukherjee, Prasanta K. and Coutinho, Kaline and Canuto, Sylvio and Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032 and Instituto de Fisica, Universidade de SaoPaulo, CP 66318, 05315-970 Sao Paulo, SP},
abstractNote = {The excitation lineshift and linewidth of the principal resonance line of Na embedded in liquid He have been obtained using combined Monte Carlo (MC) simulation and quantum mechanics (QM) calculations. The metropolis MC simulation used interatomic potentials obtained from high-level quantum mechanics results. Using the structures of the simulation statistically relevant configurations are sampled for subsequent QM calculations. The transition wavelengths for the 3s{yields}3p principal resonance line of atomic Na were obtained using time-dependent density-functional-theory calculations of the central alkali-metal atom surrounded by the first solvation shell composed of 42 He atoms. The widths are obtained by the statistical distribution of calculated transitions. Three different functionals were used. Statistically converged results using the PBE1PBE/6-311++G(d,p) give a blueshift of 14.7 nm and a width at half maximum of 7.8 nm. Similar results are obtained using the Beeke-Lee-Yang-Parr three parameter exchange functional and the Becke three-parameter exchange with the Perdew nonlocal correlation functional models. These results seem to give a reasonable statistical representation of the structure of the He cavity enclosing the host Na atom and the consequent solvent effect on the 3s{yields}3p excitation.},
doi = {10.1103/PHYSREVA.72.0},
journal = {Physical Review. A},
number = 6,
volume = 72,
place = {United States},
year = {Thu Dec 15 00:00:00 EST 2005},
month = {Thu Dec 15 00:00:00 EST 2005}
}
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