Excited-State Ions in Femtosecond Time-Resolved Mass Spectrometry: An Investigation of Highly Excited Chloroamines

被引:6
作者
Rusteika, Nerijus [1 ]
Brogaard, Rasmus Y. [1 ]
Solling, Theis I. [1 ]
Rudakov, Fedor M. [2 ]
Webert, Peter M. [2 ]
机构
[1] Univ Copenhagen, DK-2100 Copenhagen, Denmark
[2] Brown Univ, Dept Chem, Providence, RI 02912 USA
基金
新加坡国家研究基金会;
关键词
RYDBERG IONIZATION SPECTROSCOPY; DYNAMICS; NM;
D O I
10.1021/jp807227e
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
We have investigated the processes induced by femtosecond laser pulses in chloroamines, with a focus on the generation and observation of a highly reactive radical and on the involvement and general importance of excited-state ions in time-resolved mass spectrometry investigations of gaseous molecules. We have found that 280 nm femtosecond pulses lead to an ultrafast breakage of the N-Cl bond on the repulsive S, surface, and that resulting radical is long-lived. When exposing the molecule to 420 nm photons a multiphoton ionization takes place to generate ions; these ions can then be excited with a 280 nm photon. The evidence is unambiguous since we observe a distinct temporal evolution of the ion current with no photoelectrons to match. We suggest that the involvement of excited-state ions is a general phenomenon in time-resolved photoionization studies.
引用
收藏
页码:40 / 43
页数:4
相关论文
共 13 条
[1]  
[Anonymous], 1999, CHEM KINETICS DYNAMI
[2]   Computational predictions regarding ultrafast bond breakage and conformational changes in aliphatic chloro-amines [J].
Brogaard, Rasmus Y. ;
Solling, Theis I. .
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 2007, 811 (1-3) :117-124
[3]   Gaussian-3 theory using reduced Moller-Plesset order [J].
Curtiss, LA ;
Redfern, PC ;
Raghavachari, K ;
Rassolov, V ;
Pople, JA .
JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (10) :4703-4709
[4]   Femtosecond activation of reactions and the concept of nonergodic molecules [J].
Diau, EWG ;
Herek, JL ;
Kim, ZH ;
Zewail, AH .
SCIENCE, 1998, 279 (5352) :847-851
[5]   Energy flow and fragmentation dynamics of N,N-dimethylisopropylamine [J].
Gosselin, JL ;
Minitti, MP ;
Rudakov, FM ;
Solling, TI ;
Weber, PA .
JOURNAL OF PHYSICAL CHEMISTRY A, 2006, 110 (12) :4251-4255
[6]   Ultrafast electron diffraction and structural dynamics:: Transient intermediates in the elimination reaction of C2F4I2 [J].
Ihee, H ;
Goodson, BM ;
Srinivasan, R ;
Lobastov, VA ;
Zewail, AH .
JOURNAL OF PHYSICAL CHEMISTRY A, 2002, 106 (16) :4087-4103
[7]   Reassessing the orbitals of pi systems using photoinduced Ryberg ionization spectroscopy [J].
Johnson, PM ;
Anand, R ;
Hofstein, JD ;
LeClaire, JE .
JOURNAL OF ELECTRON SPECTROSCOPY AND RELATED PHENOMENA, 2000, 108 (1-3) :177-187
[8]   Photoinduced Rydberg ionization spectroscopy of phenol: The structure and assignment of the (B)over-tilde-state of the cation [J].
LeClaire, JE ;
Anand, R ;
Johnson, PM .
JOURNAL OF CHEMICAL PHYSICS, 1997, 106 (17) :6785-6794
[9]   NEW ASPECTS OF HOFMANN-LOEFFLER N-CHLORAMINE REARRANGEMENT IN ACETIC ACID [J].
NEALE, RS ;
WALSH, MR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1965, 87 (06) :1255-&
[10]   Femtosecond real-time probing of reactions .22. Kinetic description of probe absorption, fluorescence, depletion and mass spectrometry [J].
Pedersen, S ;
Zewail, AH .
MOLECULAR PHYSICS, 1996, 89 (05) :1455-1502