High-Resolution Spectroscopy of Jet-Cooled Naphthalene: the 000 and 3301 Bands of the Ã1B1←1A Transition

Joo, Duck‐Lae; Takahashi, Rika; O'Reilly, J.; Katô, Hajime; Baba, Masaaki

doi:10.1006/jmsp.2002.8625

Cited by 16 publications

(12 citation statements)

References 16 publications

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“…Table V clearly shows this to be the case for naphthalene 32 and cis-2HN, 6 as all changes in rotational constants are negative. However, in both the NH 3 6 we estimate the O−H· · ·OH 2 distance to be 1.96 Å in S 0 and 1.92 Å in S 1 .…”

Section: A S 0 and S 1 Structures Of Cis-2hnwmentioning

confidence: 80%

Flickering dipoles in the gas phase: Structures, internal dynamics, and dipole moments of β-naphthol-H2O in its ground and excited electronic states

Fleisher

Young

Pratt

et al. 2011

The Journal of Chemical Physics

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Described here are the rotationally resolved S(1)-S(0) electronic spectra of the acid-base complex cis-β-naphthol-H(2)O in the gas phase, both in the presence and absence of an applied electric field. The data show that the complex has a trans-linear O-H⋅⋅⋅O hydrogen bond configuration involving the -OH group of cis-β-naphthol and the oxygen lone pairs of the attached water molecule in both electronic states. The measured permanent electric dipole moments of the complex are 4.00 and 4.66 D in the S(0) and S(1) states, respectively. These reveal a small amount of photoinduced charge transfer between solute and solvent, as supported by density functional theory calculations and an energy decomposition analysis. The water molecule also was found to tunnel through a barrier to internal motion nearly equal in energy to kT at room temperature. The resulting large angular jumps in solvent orientation produce "flickering dipoles" that are recognized as being important to the dynamics of bulk water.

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Section: A S 0 and S 1 Structures Of Cis-2hnwmentioning

confidence: 80%

Flickering dipoles in the gas phase: Structures, internal dynamics, and dipole moments of β-naphthol-H2O in its ground and excited electronic states

Fleisher

Young

Pratt

et al. 2011

The Journal of Chemical Physics

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“…The molecule has been confirmed to be planar ͑D 2h symmetry͒ in both the S 0 1 A g and S 1 1 B 3u states. [18][19][20] All three coordinate axes are identical in the D 2h symmetry. Here we employ Pariser's notation 27 in which the in-plane long and short axes are taken as x and y, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…It has been shown that ISC is not the main radiationless process in the low excess energy region by measurement of the Zeeman splitting of rotational lines. 20,21 We have measured the Zeeman splitting of the 0 0 0 + 1380 cm −1 band and the results are shown in Fig. 4͑a͒.…”

Section: Resultsmentioning

confidence: 99%

“…On the other hand, small Zeeman splitting of rotational lines has distinctly indicated that the mixing with the triplet state is very weak. [20][21][22][23][24] Thus, the excited-state dynamics in the S 1 1 B 3u state of naphthalene remains an open question. In order to understand the dynamics in more detail, it is necessary to observe and analyze rotationally resolved high-resolution spectra of not only prominent vibronic bands but also weak bands because fluorescence quantum yield is low at the vibronic level of efficient radiationless transition.…”

Section: Introductionmentioning

confidence: 99%

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High-resolution spectroscopy of weak and short-lived bands of the S1 B13u←S A1g transition of naphthalene

Yoshida

Semba²,

Kasahara³

et al. 2009

The Journal of Chemical Physics

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Rotationally resolved high-resolution spectra and fluorescence decay curves have been observed for weak and short-lived vibronic bands of the S(1) (1)B(3u) <-- S(0) (1)A(g) transition of naphthalene. Fluorescence lifetime of the vibronic band with an excess energy of 1390 cm(-1) (0(0)(0) + 1390 cm(-1) band) is remarkably shorter than that of other bands. Zeeman splitting of rotational lines is very small, so that the main radiationless process is not intersystem crossing to the triplet state but internal conversion to the ground state. The lifetime is thought to be governed by the strength of vibronic coupling between vibrational levels of the S(0) and S(1) states. As for the 0(0)(0) + 2570 cm(-1) band, energy shifts were found in only a few rotational levels although the excess energy was higher than the threshold of intramolecular vibrational redistribution. We conclude that all of the rotational levels are mixed with other vibrational levels. The 0(0)(0) + 3068 cm(-1) band spectrum is fairly complicated with numerous rotational lines, which is attributed to strong vibronic coupling with the S(2) (1)B(2u) state.

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“…2. The rotational constants of naphthalene are A = 0.041 cm −1 , B = 0.029 cm −1 , and C = 0.104 cm −1 [111]. 1 The polarizabil- 1 In contrast to spectroscopic convention, the rotational constants A, B and C are not ordered according to magnitude.…”

Section: A Three-dimensional Alignmentmentioning

confidence: 98%

Computational studies of x-ray scattering from three-dimensionally-aligned asymmetric-top molecules

Pabst

Santra

2010

Phys. Rev. A

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We theoretically and numerically analyze x-ray scattering from asymmetric-top molecules three-dimensionally aligned using elliptically polarized laser light. A rigid-rotor model is assumed. The principal axes of the polarizability tensor are assumed to coincide with the principal axes of the moment of inertia tensor. Several symmetries in the Hamiltonian are identified and exploited to enhance the efficiency of solving the time-dependent Schrödinger equation for each rotational state initially populated in a thermal ensemble. Using a phase-retrieval algorithm, the feasibility of structure reconstruction from a quasiadiabatically aligned sample is illustrated for the organic molecule naphthalene. The spatial resolution achievable strongly depends on the laser parameters, the initial rotational temperature, and the x-ray pulse duration. We demonstrate that for a laser peak intensity of 5 TW/cm 2 , a laser pulse duration of 100 ps, a rotational temperature of 10 mK, and an x-ray pulse duration of 1 ps, the molecular structure may be probed at a resolution of 1Å. STEFAN PABST, PHAY J. HO, AND ROBIN SANTRA PHYSICAL REVIEW A 81, 043425 (2010)where the expansion coefficients [C(t)]The equation of motion for the expansion coefficients in the interaction picture (subscript I) readsIn the following, we assume we found [C L,I (t)] J 1 τ 1 M 1 J 0 τ 0 M 0 , the solution for the laser-only problem, i.e.,Ĥ rot +Ĥ L (t). Note that in the laser-only Hamiltonian no x-ray field is involved and we will drop the x-ray field indices in its solution.The interaction between the laser-aligned molecules and the x-ray field is taken into account by first-order perturbation theory. The solution of Eq. (7) becomesThe expectation values of interest can be calculated by043425-2 = − 1 2 2 J =0 J M=−J (−1) J +M [α pol ] [J ] L M U [J ] L −M (t), (18) | J τ M (t) has to be known to calculate the expectation values. However, | J τ M (t) can be written as a superposition of | J KM (t) [cf. Eq. (11)], and by using the same argument as for M, only | J KM (t) for K 0 are necessary to build all | J τ M (t) [cf. Eq. ( 13)]. This makes it attractive to propagate | J KM (t) rather than | J τ M (t) . Taking both symmetries together only the states | J KM (t) for 0 K,M J have to be propagated to understand the full system response, which can save up to a factor 4 in computational effort.The decoupling between even and odd K/τ states and M states also enhances efficiency and does not get destroyed by the presence of the interactionĤ L (t). Therefore, many [C L (t)] J τ M J KM remain zero throughout the alignment process. This holds for symmetric-top as good as for asymmetric-top rotors, since each |J τ M can be classified into the class E ± or O ± (cf. Sec. II A). The benefit is not just a speed-up by a factor 4; also the memory requirement to store [C L (t)] J τ M J KM , the matrixĤ L (t), and the matrices cos 2 θ lm is reduced by a factor 4. Memory size can become an issue on PCs when high J states are not negligible.

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High-Resolution Spectroscopy of Jet-Cooled Naphthalene: the 000 and 3301 Bands of the Ã1B1←1A Transition

Cited by 16 publications

References 16 publications

Flickering dipoles in the gas phase: Structures, internal dynamics, and dipole moments of β-naphthol-H2O in its ground and excited electronic states

Flickering dipoles in the gas phase: Structures, internal dynamics, and dipole moments of β-naphthol-H2O in its ground and excited electronic states

High-resolution spectroscopy of weak and short-lived bands of the S1 B13u←S A1g transition of naphthalene

Computational studies of x-ray scattering from three-dimensionally-aligned asymmetric-top molecules

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