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Title: Bond dissociation energy and electronic spectroscopy of Cr + (NH 3 ) and its isotopomers

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5053691· OSTI ID:1543888
 [1];  [1]; ORCiD logo [1]
  1. Univ. of Massachusetts, Amherst, MA (United States). Dept. of Chemistry
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The electronic spectra of Cr+(NH3), Cr+(ND3), and Cr+(15NH3) have been measured from 14 200 to 17 400 cm-1 using photodissociation spectroscopy. Transitions are predominantly observed from the 6A1 ground state, in which the Cr+ has a 3$$d$$5 electronic configuration, to the $$|tilde{B}$$ 6E ($$Π$$) state (3$$d$$44s). There is extensive vibronic structure in the spectrum due to a long progression in the Cr–N stretch and transitions to all six spin-orbit levels in the upper state. The spin-orbit splitting in the excited state is observed to be Aso$$'$$ = 39 cm-1. For the lowest spin-orbit level, the Cr–N stretching frequency in the excited state is 343 cm-1, with an anharmonicity of 4.2 cm-1. The 6E ($$Π$$) origin is predicted to lie at T0 = 14 697 cm-1. The first peak observed is due to v$$'$$ = 1, so the observed photodissociation onset is thermodynamic rather than spectroscopic, giving D0(Cr+-NH3) = 14 830 ± 100 cm-1 (177.4 ± 1.2 kJ/mol) and D0(Cr+–ND3) = 15 040 ± 30 cm-1 (179.9 ± 0.4 kJ/mol). The 6E ($$Π$$) state of Cr+(NH3) is ~2740 cm-1 less strongly bound than the ground state, and the Cr–N bond length increases by 0.23 ± 0.03 Å upon electronic excitation. Calculations at the time-dependent density functional theory (M06) and equations of motion coupled cluster, with single and double excitations (EOM-CCSD) level fairly accurately predict the energy and vibrational frequency of the excited state. Multi-reference configuration interaction calculations show how the spin-orbit states of Cr+(NH3) evolve into those of Cr+ + NH3.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1543888
Journal Information:
Journal of Chemical Physics, Vol. 149, Issue 17; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

References (39)

Sequential solvation of atomic transition-metal ions. The second solvent molecule can bind more strongly than the first journal May 1989
Spectroscopy and reactivity of size-selected Mg[sup +]-ammonia clusters journal January 2004
Photodissociation of size-selected aquamagnesium (Mg+(H2O)n) ions for n = 1 and 2 journal October 1992
Frequency- and time-resolved cluster photodissociation dynamics in Sr+(H2O) n , Sr+(NH3) n and Sr+(CH3OH) n journal January 1993
Spectroscopic studies of mass selected clusters of Sr+ solvated by H2O and D2O journal November 1999
Size-dependent effects in the photodissociation spectra of strontium ammine complexes (Sr+(NH3)n, n = 1-4) journal June 1989
Coordination and solvation of copper ion: infrared photodissociation spectroscopy of Cu+(NH3)n (n = 3–8) journal January 2007
Vibrational spectroscopy of ammoniated sodium ions: Na+(NH3)M, M = 6-12 journal May 1992
Vibronic spectroscopy of unsaturated transition metal complexes: CrC[sub 2]H, CrCH[sub 3], and NiCH[sub 3] journal January 2004
Theoretical Study of Two-State Reactivity of Transition Metal Cations:  The “Difficult” Case of Iron Ion Interacting with Water, Ammonia, and Methane journal February 2004
Coordination and solvation of V+ with ammonia molecules: Infrared photodissociation spectroscopy of V+(NH3)n (n=4–8) journal June 2012
Molpro: a general-purpose quantum chemistry program package: Molpro
  • Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.82
journal July 2011
Theoretical Study of Ammonia and Methane Activation by First-Row Transition Metal Cations M + (M = Ti, V, Cr) journal February 2002
Atomic spin-orbit interaction parameters from spectral data for 19 elements journal January 1974
ZEKE spectroscopy of the AgNH3 complex journal May 2003
Vibrational structure of an electrostatically bound ion–water complex journal October 1990
Dissociation Energy and Electronic and Vibrational Spectroscopy of Co + (H 2 O) and Its Isotopomers journal August 2012
Infrared photodissociation spectroscopy of [Al(NH3)n]+ (n=1–5): Solvation structures and insertion reactions of Al+ into NH3 journal February 2006
Theoretical study of ammonia activation by M+ (M=Sc, Ni, Cu) journal June 1999
A molecular picture of metal ion solvation: Infrared spectroscopy of Cu+(NH3)n and Ag+(NH3)n in the gas phase journal July 2009
Vibrationally resolved photofragment spectroscopy of FeO+ journal July 1999
Infrared photodissociation spectroscopy of Co+(NH3)n and Ni+(NH3)n: preference for tetrahedral or square-planar coordination journal January 2010
Photodissociation spectroscopy of the temperature-controlled hydrated calcium ion journal October 2011
Absorption spectra of size‐selected solvated metal cations: Electronic states, symmetries, and orbitals in Sr + (NH 3 ) 1,2 and Sr + (H 2 O) 1,2 journal March 1991
Infrared photodissociation spectroscopy of Mg+(NH3) (n=3–6): direct coordination or solvation through hydrogen bonding journal July 2004
Photodissociation spectroscopy of Zn+(H2O) and Zn+(D2O) journal February 2005
ZEKE photoelectron spectroscopy of the silver- and copper-ammonia complexes journal October 2003
Sequential Bond Dissociation Energies of M + (NH 3 ) x ( x = 1−4) for M = Ti−Cu journal April 1998
Photodissociation spectroscopy of Ca + –H 2 O and Ca + –D 2 O journal March 1996
Pulsed-field ionization electron spectroscopy and conformation of copper-diammonia journal June 2005
Photodissociation and ab initio studies of Mg+(NH3)n, n=1–4: Electronic structure and photoinduced reaction journal November 2002
Density Functional Study of Ammonia Activation by Late First-Row Transition Metal Cations journal August 2004
Cationic Noncovalent Interactions: Energetics and Periodic Trends journal March 2016
Photodissociation Studies of the Electronic and Vibrational Spectroscopy of Ni + (H 2 O) journal January 2012
An ab initio study of the reaction mechanism of Co++NH3 journal May 1997
Spectroscopically determined binding energies of CrAr+ and Cr(N2)+ journal March 1991
Near ultraviolet photodissociation spectroscopy of Mn + (H 2 O) and Mn + (D 2 O) journal November 2014
Photodissociation and photochemistry of V + (H 2 O) n , n  = 1–4, in the 360–680 nm region journal August 2012
Theoretical study of one and two ammonia molecules bound to the first-row transition metal ions journal December 1991

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