Matrix photochemistry of nitrosyl chloride.

Hallou, A.; Schriver‐Mazzuoli, L.; Schriver, A.; Chaquin, Patrick

doi:10.1016/s0301-0104(98)00238-9

Cited by 27 publications

(42 citation statements)

References 48 publications

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“…Figure 2 b shows a cut for r NO =2.15 bohr. The key features here are the two wells, one of which is at the Franck–Condon (FC) geometry and the other further out, centred at about r ClN =5.7 bohr, r NO =2.1 bohr and θ =40°, which corresponds to the ClON isomer [39]. This second well arises due to an interaction with the 2 1 A′ state occurring around θ =70° throughout the surface.…”

Section: Resultsmentioning

confidence: 92%

Photodissociation of ClNO in the 2 ¹A′ State: Computational and Experimental NO Product State Distributions

et al. 2013

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Ultrafast photodissociation of the 2 1A′ state of ClNO, which has an absorption spectrum peaking at 335 nm, is studied by computational and experimental methods. New potential-energy surfaces are calculated for the 1 and 2 1A′ states at the multireference configuration interaction (MRCI) level. Wavepacket dynamics simulations performed both exactly and by using the multiconfiguration time-dependent Hartree method yield essentially identical results. Transition dipole moments at a range of geometries are included in these calculations to correctly model the excitation. Vibrational and rotational state distributions of the NO product are obtained both computationally by analysing the quantum flux on the 2 1A′ surface and experimentally by use of 3D resonant multiphoton ionisation (REMPI), a variant of the velocity map imaging technique. The nascent NO is found to be only marginally vibrationally excited, with 91 % formed in v=0. The calculated NO rotational distribution peaks in the j=45–55 region, which compares favourably to experiment.

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Section: Resultsmentioning

confidence: 92%

Photodissociation of ClNO in the 2 ¹A′ State: Computational and Experimental NO Product State Distributions

et al. 2013

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“…25,36,[39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54][55][56] In contrast, the structural isomer (ClON) is the only photoproduct observed in low-temperature matrix studies. 63,64 The results presented here represent the first detailed measurements of ClNO photochemistry in solution. The experimentally observed opticaldensity evolution that occurs following ClNO photolysis demonstrates that a photoproduct is formed that has an absorption maximum of 295 nm in acetonitrile and 330 nm in chloroform.…”

Section: Discussionmentioning

confidence: 88%

“…Specifically, the NO-stretch fundamental transition (ν 1 ) does not change significantly between gasphase (1799.7 cm -1 ) and Ar matrixes (1805 cm -1 ); however, the bend and ClN fundamental transitions shift from 596 cm -1 (ν 2 ) and 332 cm -1 (ν 3 ) in the gas phase to 585 cm -1 (ν 2 ) and 319 cm -1 (ν 3 ) in an Ar-matrix, respectively. 63,64,82 In solution, the ν 2 and ν 3 fundamental transitions shift from 585 and 325 cm -1 in cyclohexane to 545 and 310 cm -1 in acetonitrile. 65,66 With respect to the structural isomer, ClON is predicted to have an even shorter NO bond length (1.127 Å) than diatomic NO whereas the ClO bond length is predicted to be extremely long (2.273 Å).…”

Section: Discussionmentioning

confidence: 99%

Femtosecond Pump−Probe Studies of Nitrosyl Chloride Photochemistry in Solution

2006

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We present a femtosecond pump-probe study of the primary events of nitrosyl chloride (ClNO) photochemistry in solution. Following 266 nm photolysis, the resulting evolution in optical density is measured for ClNO dissolved in acetonitrile, chloroform, and dichloromethane. The results demonstrate that photolysis results in the production of a photoproduct that has an absorption band maximum at 295 nm in acetonitrile and 330 nm in chloroform and dichloromethane. To determine the extent of Cl production, comparative photochemical studies of methyl hypochlorite (MeOCl) and ClNO are performed. Photolysis of MeOCl in solution results in the production of the Cl:solvent charge-transfer complex; therefore, a comparison of the spectral evolution observed following MeOCl and ClNO photolysis under identical photolysis conditions is performed to determine the extent of Cl production following ClNO photolysis. We find that similar to the gas-phase photochemistry, Cl and NO formation is the dominant photochemical channel in acetonitrile. However, the photochemistry in chloroform and dichloromethane is more complex, with a second product formed in addition to Cl and NO. It is proposed that in these solvents photoisomerization also occurs, resulting in the production of ClON. The results presented here represent the first detailed examination of the solution phase photochemistry of ClNO.

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“…[15][16][17][18][19] für eine Diskussion von Schweratom-Tunneleffekten in der Cyclobutadien-Automerisation (Lit. [20]) und die etwas skeptischere Sicht in Lit. [21] für Tunneleffekte in Isonitrosylchlorid sowie Lit.…”

Section: Derkürzestewegzueinemtalaufderunclassified

Sehen schwere Kerne Licht am Ende des Tunnels?

Berger

2004

Angewandte Chemie

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Matrix photochemistry of nitrosyl chloride.

Cited by 27 publications

References 48 publications

Photodissociation of ClNO in the 2 ¹A′ State: Computational and Experimental NO Product State Distributions

Photodissociation of ClNO in the 2 ¹A′ State: Computational and Experimental NO Product State Distributions

Femtosecond Pump−Probe Studies of Nitrosyl Chloride Photochemistry in Solution

Sehen schwere Kerne Licht am Ende des Tunnels?

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Matrix photochemistry of nitrosyl chloride.

Cited by 27 publications

References 48 publications

Photodissociation of ClNO in the 2 1A′ State: Computational and Experimental NO Product State Distributions

Photodissociation of ClNO in the 2 1A′ State: Computational and Experimental NO Product State Distributions

Femtosecond Pump−Probe Studies of Nitrosyl Chloride Photochemistry in Solution

Sehen schwere Kerne Licht am Ende des Tunnels?

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Photodissociation of ClNO in the 2 ¹A′ State: Computational and Experimental NO Product State Distributions

Photodissociation of ClNO in the 2 ¹A′ State: Computational and Experimental NO Product State Distributions