Electronic states and potential energy surfaces of AgH sub 2 : Comparison with AuH sub 2

Balasubramanian, K; Liao, M Z

doi:10.1021/j100338a022

Title: Electronic states and potential energy surfaces of AgH sub 2 : Comparison with AuH sub 2

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Abstract

Complete active space MCSCF (CASSCF) followed by second-order configuration interaction (SOCI) and multireference single plus double configuration interaction (MRSDCI) which include excitations from the d shells are carried out on the two low-lying states of AgH{sub 2} ({sup 2}B{sub 2} and {sup 2}A{sub 1}). The bending potential energy curves of the two states with bond lengths optimized for all angles are presented. The {sup 2}B{sub 2} surface contains a double minimum with acute and obtuse H-Ag-H angles. The {sup 2}A{sub 1} surface contains a large barrier for the insertion of an Ag({sup 2}S) atom into H{sub 2} to form the linear {sup 2}{Sigma}{sup +} state of AgH{sub 2}. The excited Ag({sup 2}P) atom spontaneously inserts into H{sub 2} to form an acute-angled weak complex of Ag with H{sub 2} and another more stable {sup 2}B{sub 2} state with obtuse bending angle. The d shell correlation lowers the {sup 2}B{sub 2} obtuse-angled structure significantly. The potential energy surfaces and electronic states of AgH{sub 2} are compared with those of AuH{sub 2}. Relativistic mass-velocity effects are significant for AuH{sub 2} in comparison to AgH{sub 2}, while d correlation effects are more significant for AgH{sub 2} in comparison to AuH{sub 2}. The Mullikenmore »« less

Authors:

Balasubramanian, K; Liao, M Z ^[1]

Arizona State Univ., Tempe (USA)

Publication Date:: Thu Jan 12 00:00:00 EST 1989

OSTI Identifier:: 5305264

DOE Contract Number:: FG02-86ER13558

Resource Type:: Journal Article

Journal Name:: Journal of Physical Chemistry; (USA)

Additional Journal Information:: Journal Volume: 93:1; Journal ID: ISSN 0022-3654

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 08 HYDROGEN; GOLD HYDRIDES; ELECTRONIC STRUCTURE; SILVER HYDRIDES; CHEMICAL BONDS; CONFIGURATION INTERACTION; POTENTIAL ENERGY; POTENTIALS; SELF-CONSISTENT FIELD; THEORETICAL DATA; DATA; ENERGY; GOLD COMPOUNDS; HYDRIDES; HYDROGEN COMPOUNDS; INFORMATION; NUMERICAL DATA; SILVER COMPOUNDS; TRANSITION ELEMENT COMPOUNDS; 400201* - Chemical & Physicochemical Properties; 080200 - Hydrogen- Storage, Transport & Handling

Citation Formats


                    Balasubramanian, K, and Liao, M Z. Electronic states and potential energy surfaces of AgH sub 2 : Comparison with AuH sub 2.  United States: N. p., 1989. 
        Web.  doi:10.1021/j100338a022.

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                    Balasubramanian, K, & Liao, M Z. Electronic states and potential energy surfaces of AgH sub 2 : Comparison with AuH sub 2.  United States.  https://doi.org/10.1021/j100338a022

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                    Balasubramanian, K, and Liao, M Z. 1989.  
        "Electronic states and potential energy surfaces of AgH sub 2 : Comparison with AuH sub 2".  United States.  https://doi.org/10.1021/j100338a022.

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@article{osti_5305264,

  title        = {Electronic states and potential energy surfaces of AgH sub 2 : Comparison with AuH sub 2},

  author       = {Balasubramanian, K and Liao, M Z},

  abstractNote = {Complete active space MCSCF (CASSCF) followed by second-order configuration interaction (SOCI) and multireference single plus double configuration interaction (MRSDCI) which include excitations from the d shells are carried out on the two low-lying states of AgH{sub 2} ({sup 2}B{sub 2} and {sup 2}A{sub 1}). The bending potential energy curves of the two states with bond lengths optimized for all angles are presented. The {sup 2}B{sub 2} surface contains a double minimum with acute and obtuse H-Ag-H angles. The {sup 2}A{sub 1} surface contains a large barrier for the insertion of an Ag({sup 2}S) atom into H{sub 2} to form the linear {sup 2}{Sigma}{sup +} state of AgH{sub 2}. The excited Ag({sup 2}P) atom spontaneously inserts into H{sub 2} to form an acute-angled weak complex of Ag with H{sub 2} and another more stable {sup 2}B{sub 2} state with obtuse bending angle. The d shell correlation lowers the {sup 2}B{sub 2} obtuse-angled structure significantly. The potential energy surfaces and electronic states of AgH{sub 2} are compared with those of AuH{sub 2}. Relativistic mass-velocity effects are significant for AuH{sub 2} in comparison to AgH{sub 2}, while d correlation effects are more significant for AgH{sub 2} in comparison to AuH{sub 2}. The Mulliken population analyses of the electronic states of AgH{sub 2} reveal considerable 5p participation. The bending potential energy surfaces of the {sup 2}B{sub 2} and {sup 2}A{sub 1} states of both the molecules cross, which would lead to avoided crossing of the {sup 2}E{sub {1/2}} components if the spin-orbit term is included. The effect of f-type polarization functions is also investigated by carrying out MRSDCI calculations which included the ten-component f functions in the basis sets.},

  doi          = {10.1021/j100338a022},

  url          = {https://www.osti.gov/biblio/5305264},
  journal      = {Journal of Physical Chemistry; (USA)},

  issn         = {0022-3654},

  number       = ,

  volume       = 93:1,

  place        = {United States},

  year         = {Thu Jan 12 00:00:00 EST 1989},

  month        = {Thu Jan 12 00:00:00 EST 1989}

}

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