The character of the longlived state formed from

The character of the long-lived state formed from S 1 of Phenylacetylene Philip M. Johnson and Trevor J. Sears Brookhaven National Laboratory and Stony Brook University Columbus Talk TK 01, Tuesday June 18 th, 2013 Support: Department of Energy Basic Energy Sciences 1

Introduction to the photophysics of substituted benzenes E(e. V) Simplified state diagram of anisole D 0 8. 0 Ion ISC, IC 5. 0 S 1, 3. 7 T 1 X Pump S 1 -T 1 gap = 1. 3 e. V (10500 cm-1) Deactivation via collisions not possible in a beam S 0 Isolated small or mediumsized aromatic. Photoexcitation can lead to a variety of processes: Fluorescence, Inter-System Crossing, Internal Conversion… Less likely: Phosphorescence, Chemistry (bond breaking) 2

Probing the collisionless photophysics E(e. V) Pump-Probe Ionization Spectroscopy Beam-cooled sample. D 0 8. 0 Ionization 5. 0 3. 7 ISC, IC Resonantly pump to S 1(v) with nsec pulsed dye laser. S 1, T 1 S 1 -T 1 gap = 1. 3 e. V (10500 cm-1) Pump S 0 Wait, then probe the system using a second (dye) laser tuned to an energy at or above the IP. Excite along the beam for longer time delays. Time-of-flight mass spectrometric detection of the ion, as parent or fragments. 3

Typical Results Instrument-limited rise S 1 Benzene v 6’=1 ISC to T 1* ISC: to excited S 0 : loss of signal 0 60 120 DELAY TIME (ns) From: J. Phys. Chem. 1988, 92, 183, Colson Group 0 2 microsecs ISC: to excited S 0 : loss of signal 4 From: J. Phys. Chem. 1983, 87, 2232 Johnson Group Biexponential decay due to singlet and triplet*. Energy in T* is important for determining its lifetime. 4

Model S 1 Benzene v 6’=1 ISC to T 1* 0 Kommandeur, Adv. Chem. Phys. 70, 133 (1988). 2 microsecs ISC: to excited S 0 : loss of signal 4 From: J. Phys. Chem. 1983, 87, 2232 Johnson Group Singlet level mixed with few levels {|k>} from a triplet state, which are themselves more weakly coupled to a set of {|l>}. |s> may also be weakly coupled to (another) set of {l>}. Solve T-D Schroedinger equation or coupled rate equations. 5

Another view Photoelectron spectra as a function of the delay time. Watch the triplet spectrum gain intensity as the singlet decays. Benzene delayed PES S 1 Triplet This confirms the longer-lived triplet is formed from the initially excited singlet in benzene. By tuning to higher S 1 states in the excitation step, one can watch the T 1 decay rate increase. 0. 0 1. 0 2. 0 Photoelectron energy/e. V 6

Phenylacetylene S 1 -S 0 spectrum has a band origin at 35877 cm-1 and, in a jet-cooled sample, is simple looking. Vibrational assignments were made by comparison to related molecules and by calculations of vibrational frequencies and intensities. Rotationally resolved spectrum of the origin band derived from high resolution LIF (Pratt group). 7

Phenylacetylene photophysics Pump-Probe delay ionization experiment. S 1 decay looks normal, but we find a longlived species that survives for as long as we can measure. Limited by the length of the beam apparatus! Fast decay (~75 ns) of S 1 state due to fluorescence Slow decay (>100 ms) of ? ? ? DELAY TIME (ns) From: J. Phys. Chem. A 2008, 112, 1195 Checked the spectrum of the long-lived species is the same as that of S 1, and it is. Spectra here at 30 ns (top), 3μs middle and calculated (bottom). 8

Photoelectron Spectra Time-dependent PES of benzene, as before. Triplet S 1 Long lifetime species 0. 0 1. 0 2. 0 Photoelectron energy/e. V Same experiment on PA. The long-lived species appears instantaneously in this experiment, and does not decay. 9

S 1 multi-exponential decay Examining the S 1 photoelectron spectrum at longer delays, one sees residual S 1 signal. Typical of intermediate sized molecules, coupling of bright state to manifold of T-states. See the same signature in fluorescence spectrum. However, the long-lived state is formed during the laser pulse and does not decay, i. e. not coupled to other states at all? 10

Summary of the observations Following excitation of the S 1 state of PA in a cold beam, we see decay of the singlet state with a multiexponential lifetime matching the known fluorescence + ISC decay and a separate, much longer-lived component. Production of the long-lived state occurs synchronously with S 1, and it has a distinct PES. By comparison with related molecules, the state energies in PA would argue for a Triplet lifetime in the 10 -100 s of ns. Benzonitrile (C 6 H 5 CN) shows similar behaviour. 11

Mass spectrometry experiments Possibilities: PA has some alternative route to a low internal energy Tn level. Or: Isomerization? Compare ion fragmentation patterns in mass spectra of S 1 and the long-lived state. Any isomer will have a different ion fragmentation pattern. Reflectron TOF used has mass resolution of >500. 12

Mass spectra The fragmentation patterns are essentially identical. Differences are due to fragmentation of metastable ions at different points along the flight path. b c d This means the long-lived state is PA in some excited electronic state, probably with low internal excitation. 13

The long-lived state observed following excitation to S 1 of PA (and, by extension benzonitrile) is not an isomer, but an excited (triplet) state with low vibrational excitation. The state is formed during the laser pulse, and does not couple to underlying continua. Signal (arb) Summary ? Probe laser delay (ns) New class of radiationless transition behavior? Raman-type process? 14

Acknowledgements Phil Johnson, Gary Lopez, Jason Hofstein, Chih-Hsuan Chang, Haifeng Xu, Greg Hall BNL, Department of Energy, for financial support. 15

Calculated state energies Δ e. V Δ cm-1 λ nm From S 0 Δ cm-1 S 1 -Tn Zero pt. corr. -au State Symm. Energy-au Δ e. V Δ cm-1 λ nm From S 0 with ZPC Expt. e. V S 0 A 1 -308. 509241335 S 1 B 2 -308. 332190987 4. 818 38858 257. 3 0. 103649 4. 663 37607 265. 9 4. 448 a T 1 A' -308. 393654958 3. 145 25368 394. 2 13490 0. 103693 2. 991 24127 414. 5 3. 154 b T 2 A 1 -308. 357574529 4. 127 33287 300. 4 5571 T 3 B 2 -308. 354502990 4. 211 33961 294. 5 4897 T 4 B 2 -308. 341191807 4. 573 36883 271. 1 1975 0. 109349 4. 255 b Gaussian-09 TD-DFT aug-cc-p. VTZ basis T 1 state has significant quinoidal structure and trans-configuration about the C-C triple bond 16

Related Work • “Fully” rotationally-resolved spectra Pratt group recorded LIF in a beam using a c. w. dye laser. This is much higher resolution than we get with the pulse-amplified c. w. system. Line widths commensurate with fluorescence lifetime. There are ‘extra’ lines in the spectrum, that may be due to triplet perturbing levels. Or something else? With our pulsed laser linewidths, they would be coherently excited in our experiment. Also, the Meijer group has recently recorded ultracold spectra of BN-and seen extra lines and shifts too. 17