The excitonic S1/S2 state splitting and the localization/delocalization of the S1 and S2 electronic states are investigated in the benzonitrile dimer (BN)2 and its (13)C and d5 isotopomers by mass-resolved two-color resonant two-photon ionization spectroscopy in a supersonic jet, complemented by calculations. The doubly hydrogen-bonded (BN-h5)2 and (BN-d5)2 dimers are C2h symmetric with equivalent BN moieties. Only the S0 → S2 electronic origin is observed, while the S0 → S1 excitonic component is electric-dipole forbidden. A single (12)C/(13)C or 5-fold h5/d5 isotopic substitution reduce the dimer symmetry to Cs, so that the heteroisotopic dimers (BN)2-(h5 – h5(13)C), (BN)2-(h5 – d5), and (BN)2-(h5 – h5(13)C) exhibit both S0 → S1 and S0 → S2 origins. Isotope-dependent contributions Δiso to the excitonic splittings arise from the changes of the BN monomer zero-point vibrational energies; these range from Δiso((12)C/(13)C) = 3.3 cm(–1) to Δiso(h5/d5) = 155.6 cm(–)1. The analysis of the experimental S1/S2 splittings of six different isotopomeric dimers yields the S1/S2 exciton splitting Δexc = 2.1 ± 0.1 cm(–1). Since Δiso(h5/d5) ≫ Δexc and Δiso((12)C/(13)C) > Δexc, complete and near-complete exciton localization occurs upon (12)C/(13)C and h5/d5 substitutions, respectively, as diagnosed by the relative S0 → S1 and S0 → S2 origin band intensities. The S1/S2 electronic energy gap of (BN)2 calculated by the spin-component scaled approximate second-order coupled-cluster (SCS-CC2) method is Δel(calc) = 10 cm(–1). This electronic splitting is reduced by the vibronic quenching factor Γ. The vibronically quenched exciton splitting Δel(calc)·Γ = Δvibron(calc) = 2.13 cm(–1) is in excellent agreement with the observed splitting Δexc = 2.1 cm(–1). The excitonic splittings can be converted to semiclassical exciton hopping times; the shortest hopping time is 8 ps for the homodimer (BN-h5)2, the longest is 600 ps for the (BN)2(h5 – d5) heterodimer.

Intermolecular dissociation energies D 0 (S 0 ) of the supersonic jet-cooled complexes of 1-naphthol (1NpOH) with cyclopentane, cyclohexane and cycloheptane are determined to within < 0.5 % using the

The vibronic spectra of strong charge-transfer complexes are often congested or diffuse and therefore difficult to analyze. We present the spectra of the π-stacked complex perylene trans-1,2-dichloroethene, which is in the limit of weak charge transfer, the electronic excitation remaining largely confined to the perylene moiety. The complex is formed in a supersonic jet, and its S0 ↔ S1 spectra are investigated by two-color resonant two-photon ionization (2C-R2PI) and fluorescence spectroscopies. Under optimized conditions, vibrationally cold (T(vib) ≈ 9 K) and well resolved spectra are obtained. These are dominated by vibrational progressions in the “hindered-rotation” Rc intermolecular vibration with very low frequencies of 11 (S0) and 13 cm(–1) (S1). The intermolecular Tz stretch and the Ra and Rb bend vibrations are also observed. The normally symmetry-forbidden intramolecular 1a(u) “twisting” vibration of perylene also appears, showing that the π- stacking interaction deforms the perylene moiety, lowering its local symmetry from D2h to D2. We calculate the structure and vibrations of this complex using six different density functional theory (DFT) methods (CAM-B3LYP, BH&HLYP, B97-D3, ωB97X-D, M06, and M06-2X) and compare the results to those calculated by correlated wave function methods (SCS-MP2 and SCS-CC2). The structures and vibrational frequencies predicted with the CAM-B3LYP and BH&HLYP methods disagree with the other calculations and with experiment. The other four DFT and the ab initio methods all predict a π-stacked “centered” structure with nearly coplanar perylene and dichloroethene moieties and intermolecular binding energies of D(e) = −20.8 to −26.1 kJ/mol. The 000 band of the S0 → S1 transition is red-shifted by δν = −301 cm(–1) relative to that of perylene, implying that the D(e) increases by 3.6 kJ/mol or 15% upon electronic excitation. The intermolecular vibrational frequencies are assigned to the calculated Rc, Tz, Ra, and Rb vibrations by comparing to the observed/calculated frequencies and S0 ↔ S1 Franck–Condon factors. Of the three TD-DFT methods tested, the hybrid-meta-GGA functional M06-2X shows the best agreement with the experimental electronic transition energies, spectral shifts, and vibronic spectra, closely followed by the ωB97X-D functional, while the M06 functional gives inferior results.

We combine femtosecond time-resolved rotational coherence spectroscopy with high-level ab initio theory to obtain accurate structural information for the nonpolar molecules cyclohexane (C(6)H(12)) and cyclohexane-d(12) (C(6)D(12)). We measured the rotational B(0) and centrifugal distortion constants D(J), D(JK) of the v = 0 states of C(6)H(12) and C(6)D(12) to high accuracy, for example, B(0)(C(6)H(12)) = 4306.08(5) MHz, as well as B(v) for the vibrationally excited states ν(32), ν(6), ν(16) and ν(24) of C(6)H(12) and additionally ν(15) for C(6)D(12). To successfully reproduce the experimental RCS transient, the overtone and combination levels 2ν(32), 3ν(32), ν(32) + ν(6), and ν(32) + ν(16) had to be included in the RCS model calculations. The experimental rotational constants are compared to those obtained at the second-order Møller-Plesset (MP2) level. Combining the experimental and calculated rotational constants with the calculated equilibrium bond lengths and angles allows determination of accurate semiexperimental equilibrium structure parameters, for example, r(e)(C-C) = 1.526 ± 0.001 Å, r(e)(C-H(axial)) = 1.098 ± 0.001 Å, and r(e)(C-H(equatorial)) = 1.093 ± 0.001 Å. The equilibrium C-C bond length of C(6)H(12) is only 0.004 Å longer than that of ethane. The effect of ring strain due to the unfavorable gauche interactions is mainly manifested as small deviations from the C-C-C, C-C-H(axial), and C-C-H(equatorial) angles from the tetrahedral value.

Using the stimulated-emission-pumping/resonant 2-photon ionization (SEP-R2PI) method, we have determined accurate intermolecular dissociation energies D of supersonic jet-cooled intermolecular complexes of 1-naphthol (1NpOH) with alkanes, 1NpOH·S, with S = methane, ethane, propane, and n-butane. Experimentally, the smaller alkanes form a single minimum-energy structure, while 1-naphthol·n-butane forms three different isomers. The ground-state dissociation energies D(S) for the complexes with propane and n-butane (isomers A and B) were bracketed within ±0.5%, being 16.71 ± 0.08 kJ/mol for S = propane and 20.5 ± 0.1 kJ/mol for isomer A and 20.2 ± 0.1 kJ/mol for isomer B of n-butane. All 1NpOH·S complexes measured previously exhibit a clear dissociation threshold in their hot-band detected SEP-R2PI spectra, but weak SEP-R2PI bands are observed above the putative dissociation onset for the methane and ethane complexes. We attribute these bands to long-lived complexes that retain energy in rotation-type intermolecular vibrations, which couple only weakly to the dissociation coordinates. Accounting for this, we find dissociation energies of D(S) = 7.98 ± 0.55 kJ/mol (±7%) for S = methane and 14.5 ± 0.28 kJ/mol (±2%) for S = ethane. The D values increase by only 1% upon S → S excitation of 1-naphthol. The dispersion-corrected density functional theory methods B97-D3, B3LYP-D3, and ωB97X-D predict that the n-alkanes bind dispersively to the naphthalene "Face." The assignment of the complexes to Face structures is supported by the small spectral shifts of the S → S electronic origins, which range from +0.5 to -15 cm. Agreement with the calculated dissociation energies D(S) is quite uneven, the B97-D3 values agree within 5% for propane and n-butane, but differ by up to 20% for methane and ethane. The ωB97X-D method shows good agreement for methane and ethane but overestimates the D(S) values for the larger n-alkanes by up to 20%. The agreement of the B3LYP-D3 D values is intermediate between the other two methods.