Isotopic variation of experimental lifetimes for the lowest 1 Pi u states of N2

Lifetimes of several (1)Pi(u) states of the three natural isotopomers of molecular nitrogen, (14)N(2), (14)N(15)N, and (15)N(2), are determined via linewidth measurements in the frequency domain. Extreme ultraviolet (XUV)+UV two-photon ionization spectra of the b (1)Pi(u)(v=0-1,5-7) and c(3) (1)Pi(u)(v=0) states of (14)N(2), b (1)Pi(u)(v=0-1,5-6) and c(3) (1)Pi(u)(v=0) states of (14)N(15)N, and b (1)Pi(u)(v=0-7), c(3) (1)Pi(u)(v=0), and o (1)Pi(u)(v=0) states of (15)N(2) are recorded at ultrahigh resolution, using a narrow band tunable XUV-laser source. Lifetimes are derived from the linewidths of single rotationally resolved spectral lines after deconvolution of the instrument function. The observed lifetimes depend on the vibrational quantum number and are found to be strongly isotope dependent.     

Selective hydrosilylation of styrene using an in situ formed platinum(1,3-dimesityl-dihydroimidazol-2-ylidene) catalyst

A highly active and selective in situ formed platinum(N-heterocyclic carbene) catalyst for the hydrosilylation of styrene with triethylsilane is described, which unlike all other known hydrosilylation catalysts, selectively yields hydrosilylation products, but (almost) no dehydrogenative silylation products.     

Frequency-mixing scheme for the production of tunable narrowband XUV radiation (91–95 nm): application to precision spectroscopy and predissociation in diatomic molecules

Tunable narrowband extreme ultraviolet radiation in the range 91–95 nm is produced by sum-frequency mixing of the outputs of a visible pulsed dye amplifier (seeded by a ring dye laser) and of a seeded second-harmonic Nd:YAG laser and subsequent frequency tripling in a gas jet of xenon. The capability of this scheme to provide tunable narrowband extreme ultraviolet radiation is demonstrated in several spectroscopic studies. The bandwidth of this system (0.01 cm^-1) is deduced from a recording of absorption spectra of the 4p⁵(²P_1/2)6d, J=1 line in krypton. The applicability of the system for gas-phase molecular spectroscopic studies is demonstrated in recordings of the Werner bands (4,0) in H₂ and (5,0) in D₂ at unprecedented absolute accuracy. Line-broadening studies are performed on the b¹_u⁺,v=5 valence state in N₂, yielding a lifetime of 210±25 ps. A singlet–triplet perturbation, giving rise to an accidental predissociation in an excited ¹ Rydberg state in carbon monoxide at an excitation energy of 107680 cm^-1, is analyzed in high resolution. PACS 42.65.Ky; 32.80.Rm; 33.20.Ni; 33.80.Gj; 42.60.By     

Lifetime and predissociation yield of 14N2 b 1Piu(v=1)

The lifetime of the b 1Piu(v=1) state in 14N2 has been determined experimentally using a laser-based pump-probe scheme and an exceptionally long lifetime of 2.61 ns was found. Semiempirical close-coupling calculations of the radiative lifetime, which include Rydberg-valence interactions in the singlet manifold, are consistent with this large value, giving a value of 3.61 ns and suggesting a predissociation yield of approximately 28% for this level of the b state.