Metal dihydride (MH2) and dimer (M2H4) structures in solid argon, neon, and hydrogen (M = Ca, Sr, and Ba):: Infrared spectra and theoretical calculations

被引：30

作者：

Wang, XF ^{[1
]}

Andrews, L ^{[1
]}

机构：

[1] Univ Virginia, Dept Chem, Charlottesville, VA 22901 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2004年 / 108卷 / 52期

关键词：

D O I：

10.1021/jp046046m

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Laser-ablated Ca, Sr, and Ba atoms were co-deposited with H-2 in excess argon, neon, and hydrogen to form alkaline-earth metal hydrides. The metal dihydrides (CaH2, SrH2, and BaH2) were identified in solid argon, neon, and hydrogen. Increasing infrared intensity in the symmetric stretching mode and electronic structure calculations show that these dihydride molecules have decreasing obtuse valence angles, respectively. These MH2 molecules also form (H-2)(n)MH2 complexes. Further dimerization of metal dihydrides gave double-bridged HCaH2CaH with D-2h symmetry and triple-bridged HSrH3Sr and HBaH3Ba with C-3v symmetry, which are confirmed by D-2 and HD isotopic substitutions and quantum chemical calculations. Bonding in heavy alkaline metal hydrides is discussed.

引用

页码：11500 / 11510

页数：11

共 59 条

[1] OPTICAL-SPECTRA OF CALCIUM ATOMS IN INERT MATRICES - NEW RED ABSORPTION FOR CA2 [J].

ANDREWS, L ;

DULEY, WW ;

BREWER, L .

JOURNAL OF MOLECULAR SPECTROSCOPY, 1978, 70 (01) :41-52

[2] Simple ortho-para hydrogen and para-ortho deuterium converter for matrix isolation spectroscopy [J].

Andrews, L ;

Wang, XF .

REVIEW OF SCIENTIFIC INSTRUMENTS, 2004, 75 (09) :3039-3044

[3] Infrared spectra of H2 molecules near H atoms trapped in solid H2 [J].

Andrews, L ;

Wang, XF .

JOURNAL OF PHYSICAL CHEMISTRY A, 2004, 108 (18) :3879-3883

[4] Infrared spectra of indium hydrides in solid hydrogen and of solid indane [J].

Andrews, L ;

Wang, XF .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (13) :1706-1709

[5] Matrix infrared spectra and density functional calculations of transition metal hydrides and dihydrogen complexes [J].

Andrews, L .

CHEMICAL SOCIETY REVIEWS, 2004, 33 (02) :123-132

[6] Infrared spectra and density functional theory calculations on transition metal nitrosyls. Vibrational frequencies of unsaturated transition metal nitrosyls [J].

Andrews, L ;

Citra, A .

CHEMICAL REVIEWS, 2002, 102 (04) :885-911

[7] Infrared spectrum of the novel electron-deficient BH4 radical in solid neon [J].

Andrews, L ;

Wang, XF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (25) :7280-7281

[8] REACTIONS OF PULSED-LASER EVAPORATED CA, SR, AND BA ATOMS WITH O-2 - INFRARED-SPECTRA OF THE METAL-OXIDES, OXIDE DIMERS, DIOXIDES, AND PEROXIDES IN SOLID ARGON [J].

ANDREWS, L ;

YUSTEIN, JT ;

THOMPSON, CA ;

HUNT, RD .

JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (26) :6514-6521

[9] AN AB-INITIO MOLECULAR-ORBITAL STUDY OF SMALL MAGNESIUM DIHALIDE CLUSTERS [J].

AXTEN, J ;

TRACHTMAN, M ;

BOCK, CW .

JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (32) :7823-7831

[10] The vibration-rotation emission spectrum of free BeH2 [J].

Bernath, PF ;

Shayesteh, A ;

Tereszchuk, K ;

Colin, R .

SCIENCE, 2002, 297 (5585) :1323-1324

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