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The L(a)-like S2 state (2A) of 4-(dimethylamino)benzonitrile was pumped at 267 nm in the gas phase at 130 degrees C. Nonresonant multiphoton ionization at 800 nm with mass-selective detection then probed the subsequent processes. Whereas ionization at the Franck-Condon geometry only gave rise to the parent ion, fragmentation increased on motion towards the charge-transfer (CT) state. This useful difference is ascribed to a geometry-dependent resonance in the ion. The time constants found are interpreted by ultrafast (approximately 68 fs) relaxation through a conical intersection to both the CT and the L(b)-type S1 state (1B). Then the population equilibrates between these two states within 1 ps. From there the molecule relaxes within 90 ps to a lower excited state which can only be a triplet state (T(n)) and then decomposes within 300 ps. Previous experiments either investigated only 1B --> CT relaxation-which does not take place in the gas phase or nonpolar solvents for energetic reasons--or, starting from S2 excitation, typically had insufficient time resolution (>1 ps) to detect the temporary charge transfer. Only recently temporary population of the CT state was found in a nonpolar solvent (Kwok et al., J. Phys. Chem. A. 2000, 104, 4188), a result fully consistent with our mechanism. We also show that S2 --> S1 relaxation does not occur vertically but involves an intermediate strong geometrical distortion, passing through a conical intersection.

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4-Aminobenzonitrile derivatives have two excited states of similar energy: besides the benzene-like L(b) state (also termed "locally excited" or LE state) one with charge-transfer (CT) character that is slightly higher in the isolated molecules. The CT state can be lowered by solvents of suitable polarity, so that dual fluorescence can be observed in them. It is controversial along which coordinate this state is displaced, although the amino-group twist is a wide-spread assumption. We investigated a number of such compounds by transient ionization in the gas phase, initially exciting the higher-lying L(a) state (S(2)). Here we briefly review the previous results on 4-(dimethylamino)benzonitrile (the prototype of this class of molecules), 4-piperidino-, pyrrolidino- and pyrrolyl-benzonitrile and compare them with new results on 4-aminobenzonitrile and on the bridged derivative N-methyl-6-cyano-1,2,3,4-tetrahydroquinoline (NMC6). Although in the latter two molecules the CT state has never been detected before, we find the same relaxation path for all compounds: From S(2), the wave packet passes through a conical intersection (CI); from there part of it reaches the S(1) (L(b)) state directly, whereas another part temporarily populates the CT state (also in NMC6), from where it goes around the CI also to the L(b) well. The wave packet directly reaching the L(b) well oscillates there along coordinates involving amino-group twist and wagging or molecular arching and a quinoidal distortion. These coordinates must be components of the CI displacement vector. A vibration involving bond-length alternation of the benzene ring is ascribed to a momentum caused by the electronic symmetry change in the CI, i.e., to the nonadiabatic coupling vector. Also the CT state involves amino-group twist, as to conclude from the anisotropy of the corresponding signal. The six-membered aliphatic ring in NMC6 hinders the twist and raises the CT state to an energy that is, however, still below the L(a) state, so that it can be temporarily populated in a barrierless process. Also in aminobenzonitrile the CT state is between L(a) and L(b) and is reached from L(a) without a barrier. The twist is rationalized by vibronic interaction with a higher state that is pi-antibonding between the amino group and the aromatic ring.