Relativistic equation-of-motion coupled-cluster method using open-shell reference wavefunction: Application to ionization potential

Journal Article · Sun Aug 21 04:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4960954· OSTI ID:22678917

Pathak, Himadri; Sasmal, Sudip; Vaval, Nayana ^[1]; Nayak, Malaya K. ^[2]; Pal, Sourav ^[3]

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1. Electronic Structure Theory Group, Physical Chemistry Division, CSIR-National Chemical Laboratory, Pune 411 008 (India)
2. Theoretical Chemistry Section, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India)
3. Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076 (India)

The open-shell reference relativistic equation-of-motion coupled-cluster method within its four-component description is successfully implemented with the consideration of single- and double- excitation approximations using the Dirac-Coulomb Hamiltonian. At the first attempt, the implemented method is employed to calculate ionization potential value of heavy atomic (Ag, Cs, Au, Fr, and Lr) and molecular (HgH and PbF) systems, where the effect of relativity does really matter to obtain highly accurate results. Not only the relativistic effect but also the effect of electron correlation is crucial in these heavy atomic and molecular systems. To justify the fact, we have taken two further approximations in the four-component relativistic equation-of-motion framework to quantify how the effect of electron correlation plays a role in the calculated values at different levels of theory. All these calculated results are compared with the available experimental data as well as with other theoretically calculated values to judge the extent of accuracy obtained in our calculations.

• OSTI ID: 22678917
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 7 Vol. 145; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ELECTRON CORRELATION
EQUATIONS OF MOTION
EXPERIMENTAL DATA
IONIZATION POTENTIAL
RELATIVISTIC RANGE
WAVE FUNCTIONS