Time-resolved Infrared Absorption Research Articles

TiO2/CdS composite hollow spheres with controlled synthesis of platinum on the internal wall for the efficient hydrogen evolution

Solar driven semiconductor photocatalytic water splitting to produce hydrogen is an extremely charming process by storing photon energy in chemical bonds. In the present study, composite semiconductor TiO2/CdS was structured into uniform and porous double-shelled hollow sphere with cocatalyst platinum selectively loaded onto the internal wall. The SEM, TEM, STEM, XRD, BET and EDS elemental distribution etc. were employed to evidence the formation of the targeted photocatalyst. It was demonstrated that the material has a high efficiency of visible-light-driven hydrogen evolution (296 μmol·h−1/10 mg) with an apparent quantum efficiency (QE) of 14.5% at wavelength of 420 nm. Comparative experiment analysis and time-resolved infrared absorption study suggested that the high photocatalytic activity of the catalyst is attributed to the vectorial electron transfer (CdS → TiO2 → Pt) and the spatial separation of reduction and oxidation active surfaces achieved by the special morphology.

Broadband infrared and Raman probes of excited-state vibrational molecular dynamics: simulation protocols based on loop diagrams

Vibrational motions in electronically excited states can be observed either by time and frequency resolved infrared absorption or by off resonant stimulated Raman techniques. Multipoint correlation function expressions are derived for both signals. Three representations which suggest different simulation protocols for the signals are developed. These are based on the forward and the backward propagation of the wavefunction, sum over state expansion using an effective vibrational Hamiltonian or a semiclassical treatment of a bath. We show that the effective temporal (Δt) and spectral (Δω) resolution of the techniques is not controlled solely by experimental knobs but also depends on the system dynamics being probed. The Fourier uncertainty ΔωΔt > 1 is never violated.

Ultrafast formation of the benzoic acid triplet upon ultraviolet photolysis and its sequential photodissociation in solution

Time-resolved infrared (TR-IR) absorption spectroscopy in both the femtosecond and nanosecond time domain has been applied to examine the photolysis of benzoic acid in acetonitrile solution following either 267 nm or 193 nm excitation. By combining the ultrafast and nanosecond TR-IR measurements, both the excited states and the photofragments have been detected and key mechanistic insights were obtained. We show that the solvent interaction modifies the excited state relaxation pathways and thus the population dynamics, leading to different photolysis behavior in solution from that observed in the gas phase. Vibrational energy transfer to solvents dissipates excitation energy efficiently, suppressing the photodissociation and depopulating the excited S(2) or S(3) state molecules to the lowest T(1) state with a rate of ∼2.5 ps after a delayed onset of ∼3.7 ps. Photolysis of benzoic acid using 267 nm excitation is dominated by the formation of the T(1) excited state and no photofragments could be detected. The results from TR-IR experiments using higher energy of 193 nm indicate that photodissociation proceeds more rapidly than the vibrational energy transfer to solvents and C-C bond fission becomes the dominant relaxation pathway in these experiments as featured by the prominent observation of the COOH photofragments and negligible yield of the T(1) excited state. The measured ultrafast formation of T(1) excited state supports the existence of the surface intersections of S(2)/S(1), S(2)/T(2), and S(1)/T(1)/T(2), and the large T(1) quantum yield of ∼0.65 indicates the importance of the excited state depopulation to triplet manifold as the key factor affecting the photophysical and photochemical behavior of the monomeric benzoic acid.

UV photodissociation dynamics of iodobenzene: Effects of fluorination

The UV photochemistry of various fluorinated iodobenzenes (4-fluoro-, 2,4-difluoro-, 3,5-difluoro-, and perfluoro-iodobenzene) has been investigated at many wavelengths by velocity map imaging, time-resolved near infrared absorption spectroscopy and (spin-orbit resolved) ab initio calculations of the ground and excited state potentials along the C-I stretch coordinate, R(C-I). The textbook description of the near UV photochemistry of CH(3)I, i.e., σ∗←n excitation to the (3)Q(0+) state, followed by direct dissociation (to yield spin-orbit excited iodine atom (I∗) products) or by non-adiabatic coupling via a conical intersection (CI) with the (1)Q(1) potential (to yield ground state iodine (I) atoms) is shown to provide a good zero-order model for aryl iodide photochemistry also. However, the aryl halides also possess occupied π and low-lying π∗ orbitals, and have lower (C(2v) or C(s)) symmetry than CH(3)I. Both of these factors introduce additional subtleties. For example, excitations to and predissociation of ππ∗ excited states provide additional routes to I products, most obviously at long UV wavelengths. nσ∗∕πσ∗ configuration mixing stabilizes the (analogue of the) (3)Q(0+) potential energy surface (PES), to an extent that scales with the degree of fluorination; the corresponding 4A(1) PES in C(6)F(5)I is actually predicted to exhibit a minimum at extended R(C-I). This has the effect of extending the long wavelength threshold for forming I∗ products. The lowered symmetry enables an additional (sloped) CI with the 5A(2) (9A(") in 2,4-difluorobenzene) PES, which provides an extra non-adiabatic route to (fast) ground state I atoms when populating the 4A(1) PES at shorter UV excitation wavelengths.

Rotational dynamics of solvated carbon dioxide studied by infrared, Raman, and time-resolved infrared spectroscopies and a molecular dynamics simulation

Rotational dynamics of solvated carbon dioxide (CO(2)) has been studied. The infrared absorption band of the antisymmetric stretch mode in acetonitrile is found to show a non-Lorentzian band shape, suggesting a non-exponential decay of the vibrational and/or rotational correlation functions. A combined method of a molecular dynamics (MD) simulation and a quantum chemical calculation well reproduces the observed band shape. The analysis suggests that the band broadening is almost purely rotational, while the contribution from the vibrational dephasing is negligibly small. The non-exponential rotational correlation decay can be explained by a simple rotor model simulation, which can treat large angle rotations of a relatively small molecule. A polarized Raman study of the symmetric stretch mode in acetonitrile gives a rotational bandwidth consistent with that obtained from the infrared analysis. A sub-picosecond time-resolved infrared absorption anisotropy measurement of the antisymmetric stretch mode in ethanol also gives a decay rate that is consistent with the observed rotational bandwidths.

Effect of Photoexcited Electron Dynamics on Photocatalytic Efficiency of Bismuth Tungstate

Photoexcited carrier dynamics of bismuth tungstate (Bi2WO6) photocatalysts was investigated by time-resolved infrared (IR) absorption spectroscopy. Monotonic absorption at the mid-IR region, which is attributable to absorption by photoexcited electrons, was monitored as a function of time delay from the microsecond to millisecond range after photoexcitation. Bi2WO6 particles with different crystalline content were prepared by hydrothermal reaction at several temperatures and used to elucidate the relation between density of photoexcited carriers and steady-state photocatalytic efficiency. Photocatalytic efficiency was tested using two reactions: oxidative decomposition of acetic acid in an aqueous solution (reaction 1) and oxidative decomposition of acetaldehyde in air (reaction 2). Crystallization of Bi2WO6 particles suppressed the fast recombination of photoexcited electrons and holes within 1 μs. In the case of crystallized particles, the density of the photoexcited electron increased with an increase in the crystalline content, and the photocatalytic efficiency for reaction 1 strongly depended on the crystalline content, indicating that photoexcited electrons remaining in the submillisecond time range significantly affect the reaction rate. On the other hand, photocatalytic efficiency for reaction 2 showed a proportional relation with specific surface area rather than crystalline content. The difference in a decisive factor depending on reaction condition is considered to be the slower rate of reaction of photoexcited electrons with molecular oxygen, which might occur within a time range between 200 μs and 3 ms over Bi2WO6.

Nσ* and πσ* excited states in aryl halide photochemistry: a comprehensive study of the UV photodissociation dynamics of iodobenzene

A recent review (Ashfold et al., Phys. Chem. Chem. Phys., 2010, 12, 1218) highlighted the important role of dissociative excited states formed by electron promotion to σ* orbitals in establishing the photochemistry of many molecular hydrides. Here we extend such considerations to molecular halides, with a particular focus on iodobenzene. Two experimental techniques (velocity mapped ion imaging (VMI) and time resolved infrared (IR) diode laser absorption) and electronic structure calculations have been employed in a comprehensive study of the near ultraviolet (UV) photodissociation of gas phase iodobenzene molecules. The VMI studies yield the speeds and angular distributions of the I((2)P(3/2)) and I*((2)P(1/2)) photofragments formed by photolysis in the wavelength range 330 ≥λ≥ 206 nm. Four distinct dissociation channels are observed for the I((2)P(3/2)) atom products, and a further three channels for the I*((2)P(1/2)) fragments. The phenyl (Ph) radical partners formed via one particular I* product channel following excitation at wavelengths 305 ≥λ≥ 250 nm are distributed over a sufficiently select sub-set of vibrational (v) states that the images allow resolution of specific I* + Ph(v) channels, identification of the active product mode (ν(10), an in-plane ring breathing mode), and a refined determination of D(0)(Ph-I) = 23,390 ± 50 cm(-1). The time-resolved IR absorption studies allow determination of the spin-orbit branching ratio in the iodine atom products formed at λ = 248 nm (ϕ(I*) = [I*]/([I] + [I*]) = 0.28 ± 0.04) and at 266 nm (ϕ(I*) = 0.32 ± 0.05). The complementary high-level, spin-orbit resolved ab initio calculations of sections (along the C-I bond coordinate) through the ground and first 19 excited state potential energy surfaces (PESs) reveal numerous excited states in the energy range of current interest. Except at the very shortest wavelength, however, all of the observed I and I* products display limiting or near limiting parallel recoil anisotropy. This encourages discussion of the fragmentation dynamics in terms of excitation to states of A(1) total symmetry and dissociation on the 2A(1) and 4A(1) (σ* ← n/π) PESs to yield, respectively, I and I* products, or via non-adiabatic coupling to other σ* ← n/π PESs that correlate to these respective limits. Similarities (and differences) with the available UV photochemical data for the other aryl halides, and with the simpler (and more thoroughly studied) iodides HI and CH(3)I, are summarised.

Comparative time-resolved study of the XeF2 etching of Mo and Si

In situ and time-resolved infrared absorption spectroscopic measurements reveal that, under typical processing conditions (∼300 K, approximately Torr pressures), XeF2 reacts efficiently but very differently with Mo and Si substrates. This kinetic study of the surface etching processes, based on the time evolution of both reactants and products, demonstrates that the mechanisms for Mo and Si etching are different. While XeF2 produces substantial roughening and a thick fluorosilyl layer on the crystalline Si surface (>200 nm), it only reacts with the surface atoms of amorphous Mo with substantially slower kinetics. The measured kinetics are quantified by simulation and the final profile experimentally obtained on etched Si surface is shown to be consistent with a recent theoretical study of the characteristic diffusion-controlled etching of silicon.

Transient infrared spectra of CH3SOO and CH3SO observed with a step-scan Fourier-transform spectrometer

A step-scan Fourier-transform spectrometer coupled with a multipass absorption cell was employed to monitor time-resolved infrared absorption of transient species produced upon irradiation at 248 nm of a flowing mixture of CH(3)SSCH(3) and O(2) at 260 K. Two transient bands observed with origins at 1397±1 and 1110±3 cm(-1) are tentatively assigned to the antisymmetric CH(3)-deformation and O-O stretching modes of syn-CH(3)SOO, respectively; the observed band contour indicates that the less stable anti-CH(3)SOO conformer likely contributes to these absorption bands. A band with an origin at 1071±1 cm(-1), observed at a slightly later period, is assigned to the S=O stretching mode of CH(3)SO, likely produced via secondary reactions of CH(3)SOO. These bands fit satisfactorily with vibrational wavenumbers and rotational contours simulated based on rotational parameters of syn-CH(3)SOO, anti-CH(3)SOO, and CH(3)SO predicted with density-functional theories B3LYP/aug-cc-pVTZ and B3P86/aug-cc-pVTZ. Two additional bands near 1170 and 1120 cm(-1) observed at a later period are tentatively assigned to CH(3)S(O)OSCH(3) and CH(3)S(O)S(O)CH(3), respectively; both species are likely produced from self-reaction of CH(3)SOO. The production of SO(2) via secondary reactions was also observed and possible reaction mechanism is discussed.

Characterization of iso-CF2I2 in frequency and ultrafast time domains

The photolysis of diiododifluoromethane (CF(2)I(2)) in condensed phases was studied by a combination of matrix isolation and ultrafast time-resolved spectroscopy, in concert with ab initio calculations. Photolysis at wavelengths of 355 or 266 nm of CF(2)I(2):Ar samples (1:5000) held at approximately 8 K yielded iso-CF(2)I(2) (F(2)C-I-I), a metastable isomer of CF(2)I(2), characterized here for the first time. The infrared (IR) spectra of this isomer were recorded in matrix experiments, and the derived positions of the C-F stretching modes are in very good agreement with the predictions of high level ab initio calculations, which show that the iso-form is a minimum on the CF(2)I(2) ground state potential energy surface. The formation of this isomer following 350 nm excitation of CF(2)I(2) in room temperature CCl(4) solutions was monitored through its intense C-F stretching mode by means of ultrafast time-resolved IR absorption. Together, matrix isolation and ultrafast IR absorption experiments suggest that the formation of iso-CF(2)I(2) occurs via recombination of CF(2)I radical and I atom. Ultrafast IR experiments detect a delayed rise of iso-CF(2)I-I absorption, placing an upper limit of 400 fs for the C-I bond dissociation and primary geminate recombination processes. The product absorption spectrum recorded 1 ns after 350 nm excitation of CF(2)I(2) in solution is virtually identical to the visible absorption spectrum of iso-CF(2)I(2) trapped in matrix isolation experiments [with subtracted I(2)(X) absorption]. The formation of this isomer in solution at room temperature has direct dynamic implications for the ultrafast production of molecular iodine from electronically excited CF(2)I(2).

Ultrafast time-resolved transient infrared and resonance Raman spectroscopic study of the photo-deprotection and rearrangement reactions of p-hydroxyphenacyl caged phosphates

This is a picosecond and nanosecond time-resolved infrared absorption spectroscopic study of p-hydroxphenacyl diethylphosphate (HPDP) in aqueous solution examining the deprotection reaction and subsequent evolution to produce the p-hydroxyphenylacetic acid (HPAA) rearrangement product. The data reported here support previous ultrafast fluorescence, Raman and transient UV/visible absorption studies and provide new insight into the role of water in the deprotection reaction. It also provides insight into the nature of the intermediate steps that take place following initial formation of the triplet state and its reaction with water to eventually produce the solvent-separated ions and solvolytic reaction product HPAA. In addition, density functional theory (DFT) calculations were performed to investigate the reactions of the triplet state of HPDP with water molecules to induce deprotection, the formation of a contact ion pair and the subsequent intermediates that lead to the HPAA rearrangement product. A more detailed reaction mechanism is proposed based on the time-resolved spectroscopy experiments and DFT computational results.

Dynamics of CO Oxidation on a Polycrystalline Platinum Electrode: A Time-Resolved Infrared Study

Electro-oxidation of CO adsorbed on a polycrystalline Pt electrode in the potential region of hydrogen absorption is examined by fast time-resolved surface-enhanced infrared absorption spectroscopy coupled to voltammetry or chronoamperometry. Oxidation dynamics at a weak preoxidation peak around 0.5 V (vs RHE) and the main oxidation peak around 0.7 V observed in stripping voltammetry are focused. IR spectra show that the shift of bridge-bonded CO to atop sites triggers the partial oxidation of CO adsorbed at atop sites to yield the preoxidation peak. It is also shown that CO on terraces becomes very mobile in the main oxidation region after some amount of CO being oxidized via a nucleation-and-growth mechanism and that terrace CO is oxidized faster than CO adsorbed at step edges. The result is interpreted in terms of a Langmuir−Hinshelwood type mechanism involving adsorbed CO and an oxygen-containing species (most likely OH) adsorbed at steps. The oxidation mechanism is essentially identical to that proposed in some earlier studies, but more convincing spectroscopic evidence of the mechanism is presented.

Picosecond time-resolved infrared absorption study on photoexcited dynamics of regioregular poly(3-hexylthiophene)

Picosecond time-resolved infrared absorption spectra of the photoexcited states of a spin-coated film of regioregular poly(3-hexylthiophene) (RR-P3HT) have been recorded at 77 K. The time-resolved photoinduced infrared absorptions due to electronic transitions at 2500 cm −1 and vibrational transitions at 1575 cm −1 have fast and slow decay components. By comparing the picosecond time-resolved infrared absorption spectrum of long-lived (slow decay component) transient species with the doping-induced infrared difference spectrum of RR-P3HT, the long-lived transient species are assigned to polarons. The short-lived transient species are assigned to singlet excitons and/or polaron pairs.

Electron Transfer Kinetics of Cytochrome C in the Submillisecond Time Regime Using Time-Resolved Surface-Enhanced Infrared Absorption Spectroscopy

The two-layer gold surface developed before is used for time-resolved surface-enhanced infrared absorption spectroscopy (tr-SEIRAS). The electron transfer (eT) rate to cytochrome c adsorbed to a self-assembled monolayer of 2-mercaptoethanol is measured using SEIRAS in the step-scan mode in an ATR configuration. Electron transfer is triggered by periodic potential pulses applied to the gold surface which is used both as an electrode and a surface enhancing layer. Phase sensitive detection is used to separate and determine band parameters of the strongly overlapping absorption bands of the amide region. The surface enhancement effect of the two-layer gold surface was determined to be 128. Rate constants for eT under conditions of the experiment were determined by tr-SEIRAS to be kox ) 1810 ( 239 s -1 and kred ) 1880 ( 232 s -1 for oxidation and reduction, respectively. This was deduced from the time-dependent change of one particular amino acid (His18) directly ligated to the porphyrine ring of the heme center. Different groups of the peptide backbone were found to be excited at different excitation frequencies.

Visible Light Responsive Pristine Metal Oxide Photocatalyst: Enhancement of Activity by Crystallization under Hydrothermal Treatment

Photocatalytic activities of amorphous and crystal bismuth tungstate (Bi(2)WO(6)) were investigated using oxidative decomposition of gaseous acetaldehyde under visible light irradiation (>400 nm). Here, for the first time, negligible photocatalytic activity of amorphous Bi(2)WO(6) owing to the fast recombination of electron-hole pairs and the high quantum efficiency of Bi(2)WO(6) crystallites under visible light were demonstrated by action spectrum analysis and time-resolved infrared absorption measurements. Crystallization of the amorphous phase provided a red shift of the photoabsorption edge and marked increase in the lifetime of photoexcited electrons, resulting in an increase of photocatalytic activity.

Picosecond Time-Resolved Polarized Infrared Spectroscopic Study of Photoexcited States and Their Dynamics in Oriented Poly(p-phenylenevinylene)

The picosecond time-resolved polarized infrared absorption spectra of the photoexcited states of an oriented poly(p-phenylenevinylene) [-(C6H4CH=CH)n-, PPV] film have been recorded in the 3600-1050 cm(-1) region. The time-resolved photoinduced infrared absorptions due to an electronic transition in the wavenumber region of 3600-1700 cm(-1) and vibrational transitions in the region of 1700-1050 cm(-1) have fast and slow decay components under all polarization conditions of the pump and probe pulses with respect to the orientation of PPV. The picosecond time-resolved infrared absorption spectra are analyzed by reference to the photoinduced and doping-induced infrared difference spectra of PPV. The long-lived transient species, observed with the pump polarization perpendicular and the probe polarization parallel to the orientation of PPV, are assigned to positive and negative polarons. The short-lived transient species under the same polarization condition is assigned to bound polaron pairs. It is likely that singlet excitons are observed with both the pump and probe polarizations parallel to the orientation of PPV. The singlet excitons show fast decay due to the exciton-exciton annihilation under the high excitation density used in the present study.

Ultrafast Excited State Dynamics of Pt(II) Chromophores Bearing Multiple Infrared Absorbers

The paper reports the synthesis, structural characterization, electrochemistry, ultrafast time-resolved infrared (TRIR) and transient absorption (TA) spectroscopy associated with two independent d (8) square planar Pt(II) diimine chromophores, Pt(dnpebpy)Cl 2 ( 1) and Pt(dnpebpy)(C[triple bond]Cnaph) 2 ( 2), where dnpebpy = 4,4'-(CO 2CH 2- (t) Bu) 2-2,2'-bipyridine and CCnaph = naphthylacetylide. The neopentyl ester substitutions provided markedly improved complex solubility relative to the corresponding ethyl ester which facilitates synthetic elaboration as well as spectroscopic investigations. Following 400 nm pulsed laser excitation in CH 2Cl 2, the 23 cm (-1) red shift in the nu C=O vibrations in 1 are representative of a complex displaying a lowest charge-transfer-to-diimine (CT) excited state. The decay kinetics in 1 are composed of two time constants assigned to vibrational cooling of the (3)CT excited-state concomitant with its decay to the ground state (tau = 2.2 +/- 0.4 ps), and to cooling of the formed vibrationally hot ground electronic state (tau = 15.5 +/- 4.0 ps); we note that an assignment of the latter to a ligand field state cannot be excluded. Ultrafast TA data quantitatively support these assignments yielding an excited-state lifetime of 2.7 +/- 0.4 ps for the (3)CT excited-state of 1 and could not detect any longer-lived species. The primary intention of this study was to develop a Pt (II) complex ( 2) bearing dual infrared spectroscopic tags (C[triple bond]C attached to the metal and CO (ester) attached to the diimine ligand) to independently track the movement of charge density in different segments of the molecule following pulsed light excitation. Femtosecond laser excitation of 2 in CH 2Cl 2 at 400 nm simultaneously induces a red-shift in both the nu C=O (-30 cm (-1)) and the nu C[triple bond]C (-61 cm (-1)) vibrations. The TRIR data in 2 are consistent with a charge transfer assignment, and the significant decrease of the energy of the nu C[triple bond]C vibration suggests a considerable contribution from the acetylide ligands in the highest occupied molecular orbital. Therefore, we assign the lowest energy optical transitions in 2 as a combination of metal-to-ligand and ligand-to-ligand charge transfers. The excited-state of 2 is emissive at RT, with an emission maximum at 715 nm, quantum yield of 0.0012, and lifetime of 23 ns.

Time‐dependent density functional theory study on hydrogen‐bonded intramolecular charge‐transfer excited state of 4‐dimethylamino‐benzonitrile in methanol

The time-dependent density functional theory (TDDFT) method was carried out to investigate the hydrogen-bonded intramolecular charge-transfer (ICT) excited state of 4-dimethylaminobenzonitrile (DMABN) in methanol (MeOH) solvent. We demonstrated that the intermolecular hydrogen bond C[triple bond]N...H-O formed between DMABN and MeOH can induce the C[triple bond]N stretching mode shift to the blue in both the ground state and the twisted intramolecular charge-transfer (TICT) state of DMABN. Therefore, the two components at 2091 and 2109 cm(-1) observed in the time-resolved infrared (TRIR) absorption spectra of DMABN in MeOH solvent were reassigned in this work. The hydrogen-bonded TICT state should correspond to the blue-side component at 2109 cm(-1), whereas not the red-side component at 2091 cm(-1) designated in the previous study. It was also demonstrated that the intermolecular hydrogen bond C[triple bond]N...H-O is significantly strengthened in the TICT state. The intermolecular hydrogen bond strengthening in the TICT state can facilitate the deactivation of the excited state via internal conversion (IC), and thus account for the fluorescence quenching of DMABN in protic solvents. Furthermore, the dynamic equilibrium of these electronically excited states is explained by the hydrogen bond strengthening in the TICT state.

Electrocatalytic Oxidation of Formaldehyde on Platinum under Galvanostatic and Potential Sweep Conditions Studied by Time-Resolved Surface-Enhanced Infrared Spectroscopy

When formaldehyde is oxidized on a Pt electrode under galvanostatic (constant current) conditions, the electrode potential oscillates spontaneously. The oscillatory behavior has been examined by time-resolved surface-enhanced infrared absorption spectroscopy (SEIRAS) for understanding the mechanism and kinetics of the reaction at the molecular scale. SEIRAS reveals that CO and formate are adsorbed on the electrode surface and that their band intensities (coverages) oscillate synchronously with the oscillation of potential. SEIRAS coupled to cyclic voltammetry or linear sweep voltammetry suggests that formaldehyde is oxidized to CO2 via two parallel processes: the direct path via adsorbed formate and the indirect path via adsorbed CO. The two processes are kinetically coupled and autocatalytically activate and deactivate formaldehyde oxidation to yield the potential oscillations. The oxidation of the electrode surface also contributes to the oscillations for large applied currents.

Solvent effects on the charge transfer excited states of 4-dimethylaminobenzonitrile (DMABN) and 4-dimethylamino-3,5-dimethylbenzonitrile (TMABN) studied by time-resolved infrared spectroscopy: a direct observation of hydrogen bonding interactions

Time-resolved infrared absorption spectra of the C[triple bond]N bands of photoexcited TMABN and DMABN have been measured in non-polar hexane, polar aprotic THF and polar protic butanol with high temporal and spectral resolution (<0.5 ps and 5 cm(-1), respectively). In butanol, the intramolecular charge transfer (ICT) state C[triple bond]N infrared absorption bands of DMABN and TMABN both develop from an initial singlet into a doublet, demonstrating the co-existence of two charge transfer excited states, one of which is hydrogen-bonded and the other similar to the state formed in aprotic solvents. The ICT C[triple bond]N absorption band of TMABN is already strong at the earliest measurement time of 2 ps in THF, hexane, and butanol, indicating prompt population of ICT by a barrierless process, as expected from the pre-twisted structure of this molecule. There are little or no subsequent fast kinetics in hexane and THF but the signal observed in butanol continues to grow substantially at later times, prior to decay, indicating population transfer from a second state excited at 267 nm. No CN absorption band attributable to this state is observed, consistent with it being similar to the LE state of DMABN. The kinetics of the later stages of the hydrogen-bonding of both DMABN and TMABN in butanol takes place on timescales consistent with known values for dipolar solvation relaxation and result in a ratio of the hydrogen-bonded to non-bonded species of approximately 3 : 1 at equilibrium for both molecules. The contrast between the prompt population of the charge transfer state of TMABN in all three solvents and charge transfer rates in DMABN limited to 13 ps(-1) in THF and 9 ps(-1) in butanol is fully consistent with the TICT description for the ICT state structure.