Infrared spectra of the WH4(H2)4 complex in solid hydrogen

Xuefeng Wang; Lester Andrews; Ivan Infante; Laura Gagliardi

doi:10.1021/ja077322o

Infrared spectra of the WH₄(H₂)₄ complex in solid hydrogen

Xuefeng Wang
, Lester Andrews
, Ivan Infante
, Laura Gagliardi

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

33 Scopus citations

Abstract

The codeposition of laser-ablated tungsten atoms with neat hydrogen at 4 K forms a single major product with a broad 2500 cm^-1 and sharp 1860, 1830, 1782, 1008, 551, and 437 cm^-1 absorptions, which are assigned to the WH₄(H₂)₄ complex on the basis of isotopic shifts and agreement with isotopic frequencies calculated by density functional theory. This D_2d structured complex was computed earlier to form exothermically from W atoms and hydrogen molecules. Annealing the matrix allows hydrogen to evaporate and the complex to aggregate and ultimately to decompose. Comparison of the H-H stretching mode at 2500 cm^-1 and the W-H₂ stretching mode at 1782 cm^-1 with 2690 and 1570 cm^-1 values for the Kubas complex W(CO)₃(PR ₃)₂(H₂) suggests that the present physically stable WH₄(H₂)₄ complex has more strongly bound dihydrogen ligands. Our CASPT2 calculations suggest a 15 kcal/mol average binding energy per dihydrogen molecule in the WH₄(H₂) ₄ complex.

Original language	English (US)
Pages (from-to)	1972-1978
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	130
Issue number	6
DOIs	https://doi.org/10.1021/ja077322o
State	Published - Feb 13 2008

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title = "Infrared spectra of the WH4(H2)4 complex in solid hydrogen",

abstract = "The codeposition of laser-ablated tungsten atoms with neat hydrogen at 4 K forms a single major product with a broad 2500 cm-1 and sharp 1860, 1830, 1782, 1008, 551, and 437 cm-1 absorptions, which are assigned to the WH4(H2)4 complex on the basis of isotopic shifts and agreement with isotopic frequencies calculated by density functional theory. This D2d structured complex was computed earlier to form exothermically from W atoms and hydrogen molecules. Annealing the matrix allows hydrogen to evaporate and the complex to aggregate and ultimately to decompose. Comparison of the H-H stretching mode at 2500 cm-1 and the W-H2 stretching mode at 1782 cm-1 with 2690 and 1570 cm-1 values for the Kubas complex W(CO)3(PR 3)2(H2) suggests that the present physically stable WH4(H2)4 complex has more strongly bound dihydrogen ligands. Our CASPT2 calculations suggest a 15 kcal/mol average binding energy per dihydrogen molecule in the WH4(H2) 4 complex.",

author = "Xuefeng Wang and Lester Andrews and Ivan Infante and Laura Gagliardi",

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T1 - Infrared spectra of the WH4(H2)4 complex in solid hydrogen

AU - Wang, Xuefeng

AU - Andrews, Lester

AU - Infante, Ivan

AU - Gagliardi, Laura

PY - 2008/2/13

Y1 - 2008/2/13

N2 - The codeposition of laser-ablated tungsten atoms with neat hydrogen at 4 K forms a single major product with a broad 2500 cm-1 and sharp 1860, 1830, 1782, 1008, 551, and 437 cm-1 absorptions, which are assigned to the WH4(H2)4 complex on the basis of isotopic shifts and agreement with isotopic frequencies calculated by density functional theory. This D2d structured complex was computed earlier to form exothermically from W atoms and hydrogen molecules. Annealing the matrix allows hydrogen to evaporate and the complex to aggregate and ultimately to decompose. Comparison of the H-H stretching mode at 2500 cm-1 and the W-H2 stretching mode at 1782 cm-1 with 2690 and 1570 cm-1 values for the Kubas complex W(CO)3(PR 3)2(H2) suggests that the present physically stable WH4(H2)4 complex has more strongly bound dihydrogen ligands. Our CASPT2 calculations suggest a 15 kcal/mol average binding energy per dihydrogen molecule in the WH4(H2) 4 complex.

AB - The codeposition of laser-ablated tungsten atoms with neat hydrogen at 4 K forms a single major product with a broad 2500 cm-1 and sharp 1860, 1830, 1782, 1008, 551, and 437 cm-1 absorptions, which are assigned to the WH4(H2)4 complex on the basis of isotopic shifts and agreement with isotopic frequencies calculated by density functional theory. This D2d structured complex was computed earlier to form exothermically from W atoms and hydrogen molecules. Annealing the matrix allows hydrogen to evaporate and the complex to aggregate and ultimately to decompose. Comparison of the H-H stretching mode at 2500 cm-1 and the W-H2 stretching mode at 1782 cm-1 with 2690 and 1570 cm-1 values for the Kubas complex W(CO)3(PR 3)2(H2) suggests that the present physically stable WH4(H2)4 complex has more strongly bound dihydrogen ligands. Our CASPT2 calculations suggest a 15 kcal/mol average binding energy per dihydrogen molecule in the WH4(H2) 4 complex.

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UR - https://www.scopus.com/pages/publications/39049156004#tab=citedBy

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 6

ER -

Infrared spectra of the WH₄(H₂)₄ complex in solid hydrogen

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