Photodissociation spectroscopy of Ca+–H2O and Ca+–D2O

Scurlock, C. T.; Pullins, S. H.; Reddic, J. E.; Duncan, M. A.

doi:10.1063/1.471206

Cited by 87 publications

(69 citation statements)

References 45 publications

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“…The measured spectra are consistent with this result. 6,13,44 These results are also verified by new simulations of the spectra of Ca + (H 2 O) and Zn + (H 2 O), with ε aa = ± 1 cm −1 are nearly identical to those with ε aa = 0. For Mn + (H 2 O), ε aa is initially set to zero because the 7 S 3 ground state of Mn + has no spin-orbit coupling.…”

Section: 12supporting

confidence: 65%

“…Although similar p x ,p y ← s transitions have been observed in Mg + (H 2 O), Ca + (H 2 O) and Zn + (H 2 O), the p z ← s has not. 6,13,37 In the spectra there are also short progressions in two other intermolecular vibrations. Their assignment is facilitated by considering the rotational structure.…”

Section: A Electronic Spectroscopymentioning

confidence: 99%

“…This increase in the HOH for states with shorter metal ion-oxygen bonds has also been observed in M + (H 2 O) (M = Mg, Ca, Co, Ni, Zn). 6,[11][12][13]37 In bare H 2 O, the HOH is 104.5…”

Section: 12mentioning

confidence: 99%

“…This is slightly larger than the ∼0.13 Å shortening observed for the analogous transition in Zn + (H 2 O) and 0.09 Å in Ca + (H 2 O). 6,13 The bond length decrease is due to repulsion between the electron in the singly occupied 4s orbital and the lone pairs on the oxygen. Promotion of this electron to the 4p x or 4p y orbital, both of which are perpendicular to the ligand, reduces this repulsion and leads to a shorter, stronger Mn + -H 2 O bond.…”

Section: A Electronic Spectroscopymentioning

confidence: 99%

“…Transitions to one quantum of ν 4 are vibronically allowed for the second excited state and would show parallel structure, but they are not observed in this case, although they are seen in Zn + (H 2 O) and Ca + (H 2 O). 6,13 Time-dependent DFT calculations are carried out to further characterize the outof-plane bend in the ground and excited electronic states of Mn + (H 2 O). The potentials are calculated by scanning the outof-plane angle from 0…”

Section: A Electronic Spectroscopymentioning

confidence: 99%

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Near ultraviolet photodissociation spectroscopy of Mn+(H2O) and Mn+(D2O)

Pearson

Copeland

Kocak

et al. 2014

The Journal of Chemical Physics

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excited states with T 0 = 30 210 and 32 274 cm −1 , respectively. Each electronic transition has partially resolved rotational and extensive vibrational structure with an extended progression in the metal−ligand stretch at a frequency of ∼450 cm −1 . There are also progressions in the in-plane bend in the 7 B 2 state, due to vibronic coupling, and the out-of-plane bend in the 7 B 1 state, where the calculation illustrates that this state is slightly non-planar. Electronic structure computations at the CCSD(T)/aug-cc-pVTZ and TD-DFT B3LYP/6-311++G(3df,3pd) level are also used to characterize the ground and excited states, respectively. These calculations predict a ground state Mn-O bond length of 2.18 Å. Analysis of the experimentally observed vibrational intensities reveals that this bond length decreases by 0.15 ± 0.015 Å and 0.14 ± 0.01 Å in the excited states. The behavior is accounted for by the less repulsive p x and p y orbitals causing the Mn + to interact more strongly with water in the excited states than the ground state. The result is a decrease in the Mn-O bond length, along with an increase in the H-O-H angle. The spectra have well resolved K rotational structure. Fitting this structure gives spin-rotation constants ε aa = −3 ± 1 cm −1 for the ground state and ε aa = 0.5 ± 0.5 cm −1 and aa = −4.2 ± 0.7 cm −1 for the first and second excited states, respectively, and A = 12.8 ± 0.7 cm −1 for the first excited state. Vibrationally mediated photodissociation studies determine the O-H antisymmetric stretching frequency in the ground electronic state to be 3658 cm −1 .

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Section: 12supporting

confidence: 65%

Section: A Electronic Spectroscopymentioning

confidence: 99%

“…This increase in the HOH for states with shorter metal ion-oxygen bonds has also been observed in M + (H 2 O) (M = Mg, Ca, Co, Ni, Zn). 6,[11][12][13]37 In bare H 2 O, the HOH is 104.5…”

Section: 12mentioning

confidence: 99%

Section: A Electronic Spectroscopymentioning

confidence: 99%

Section: A Electronic Spectroscopymentioning

confidence: 99%

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