Photodissociation study of ethyl bromide in the ultraviolet range by the ion-velocity imaging technique.

The photodissociation of ethyl bromide has been studied in the wavelength range of 231-267 nm by means of the ion velocity imaging technique coupled with a [2+1] resonance-enhanced multiphoton ionization (REMPI) scheme. The velocity distributions for the Br ((2)P(1/2)) (denoted Br*) and Br ((2)P(3/2)) (denoted Br) fragments are determined, and each can be well-fitted by a narrow single-peaked Gaussian curve, which suggests that the bromine fragments are generated as a result of direct dissociation via repulsive potential-energy surfaces (PES). The recoil anisotropy results show that beta(Br) and beta(Br*) decrease with the wavelength, and the angular distributions of Br* suggest a typical parallel transition. The product relative quantum yields at two different wavelengths are Phi(234nm)(Br*)=0.17 and Phi(267nm)(Br*)=0.31. The relative fractions of each potential surface for the bromine fragments' production at 234 and 267 nm reveal the existence of a curve crossing between the (3)Q(0) and (1)Q(1) potential surfaces, and the probability of curve crossing decreases with the laser wavelength. The symmetry reduction of C(2)H(5)Br from C(3v) to C(s) invokes a nonadiabatic coupling between the (3)Q(0) and (1)Q(1) states, and with higher energy photons, the probability that crossing will take place increases.     

离子速度成像方法研究C8H17Br分子的光解动力学

用离子速度成像方法, 研究了长链C8H17Br分子在234 nm激光下的光解过程. 通过2+1共振增强多光子电离探测了两种光解产物Br*(2P1/2)和Br(2P3/2), 得到了它们的相对量子产率. 从光解产物Br*(2P1/2)和Br(2P3/2)的速度图像得到了能量和角度分布. 并根据相对量子产率和角度分布, 计算了不同解离通道的比例. 实验发现C8H17Br分子解离过程中大部分能量都转化为内能, 该能量分配可以较好地用软反冲模型来解释, 并分析了这种能量分配跟烷基大小的关系.     

离子速度影像法研究n-C7H15Br分子光解反应动力学

利用离子速度成像方法, 研究n-C7H15Br分子在231～239 nm范围内几个波长处的光解离动力学. 通过同一束激光经(2+1)共振多光子电离(REMPI)过程探测光解碎片Br(2P3/2)和Br*(2P1/2), 得到了不同激光波长处的离子速度分布图像, 从而获得C7H15Br光解产物的能量分配和角度分布. 结合各向异性参数和量子产率, 计算了n-C7H15Br分子在234 nm波长下不同解离通道的比例. 实验表明光解产物的能量分配可以用冲击模型中的软碰撞模型来解释. 实验还发现, 各向异性参数β(Br*)的值对光波长变化很敏感, 这是由电子激发态的绝热和非绝热过程决定的.     

邻溴甲苯在234和267 nm的光解动力学

利用离子速度影像技术结合共振增强多光子电离(REMPI)技术, 研究了邻溴甲苯在234和267 nm激光作用下的光解机理. 平动能分布表明, 基态Br(2P3/2)和自旋轨道激发态Br*(2P1/2)产生于两个解离通道: 快通道和慢通道. 快通道的各向异性参数在234 nm分别为1.15(Br)和0.55(Br*), 在267 nm分别为0.90(Br)和0.60(Br*). 慢通道的各向异性参数在234 nm分别为0.12(Br)和0.14(Br*), 在267 nm分别为0.11(Br)和0.10(Br*). 源自于慢通道的Br和Br*碎片的各向异性弱于快通道. Br(2P3/2)的相对量子产率Φ(Br)在234 nm为0.67, 在267 nm为0.70. 邻溴甲苯在234 和267 nm光解主要产生基态产物Br(2P3/2). 快通道产生于(π, π*)束缚单重态被激发, 随后通过排斥性(n, σ*)态的预解离. 慢通道各向异性参数接近零, 由此证实慢通道来源于单重激发态内转换到高振动基态而引发的热解离.     

Direct observation of the primary and secondary C-Br bond cleavages from the 1,2-dibromopropane photodissociation at 234 and 265 nm using the velocity map ion imaging technique

Photodissociation dynamics of 1,2-dibromopropane has been investigated at 234 and 265 nm by using the velocity map ion imaging method. At both pump energies, a single Gaussian-shaped speed distribution is observed for the Br*((2)P(1/2)) fragment, whereas at least three velocity components are found to be existent for the Br((2)P(3/2)) product. The secondary C-Br bond cleavage of the bromopropyl radical which is energized from the ultrafast primary C-Br bond rupture should be responsible for the multicomponent translational energy distribution at the low kinetic energy region of Br((2)P(3/2)). The recoil anisotropy parameter (beta) of the fragment from the primary C-Br bond dissociation is measured to be 0.53 (0.49) and 1.26 (1.73) for Br((2)P(3/2)) and Br*((2)P(1/2)), respectively, at 234 (265) nm. The beta value of Br((2)P(3/2)) from the secondary C-Br bond dissociation event at 265 nm is found to be 0.87, reflecting the fact that the corresponding Br((2)P(3/2)) fragment carried the initial vector component of the bromopropyl radical produced from the primary bond dissociation event. Density functional theory has been used to calculate energetics involved both in the primary and in the secondary C-Br bond dissociation dynamics.     

Photodissociation of cyclobutyl bromide at 234 nm studied using velocity map imaging

This study investigates the 234 nm photodissociation dynamics of cyclobutyl bromide using a two-dimensional photofragment velocity imaging technique. The spin-orbit ground- and excited-state Br(2P) atoms are state-selectively detected via [2+1] resonance enhanced multiphoton ionization (REMPI), whereas the cyclobutyl radicals are ionized using 157 nm laser light. The Br(2P(3/2)) and the Br(2P(1/2)) atoms and their c-C4H7 radical cofragments evidence a single-peaked, Gaussian-shaped translational energy distribution ranging from approximately 14 to approximately 39 kcal/mol and angular distributions with significant parallel character. The Br(2P(1/2))/ Br(2P(3/2)) spin-orbit branching ratio is determined to be 0.11 +/- 0.07 by momentum match between the Br(2P) photofragments and the recoiling c-C4H7 fragments, assuming a uniform photoionization probability of the c-C4H7 radicals with an internal energy range of 10-35 kcal/mol. The REMPI line strength ratio for the detection of Br(2P(3/2)) and Br(2P(1/2)) atoms at 233.681 and 234.021 nm, respectively, is therefore derived to be 0.10 +/- 0.07. The measured recoil kinetic energies of the c-C4H7 radicals, and the resulting distribution of internal energies, indicates some of the radicals are formed with total internal energies above the barrier to isomerization and subsequent dissociation, but our analysis indicates they may be stable due to the substantial fraction of the internal energy which is partitioned to rotational energy of the radicals.     

Photodissociation dynamics of allyl bromide at 234, 265, and 267 nm

The photodissociation dynamics of allyl bromide was investigated at 234, 265, and 267 nm. A two-dimensional photofragment ion velocity imaging technique coupled with a [2+1] resonance-enhanced multiphoton ionization scheme was utilized to obtain the angular and translational energy distributions of the nascent Br* (2P1/2) and Br (2P3/2) atoms. The Br fragments show a bimodal translational energy distribution, while the Br* fragments reveal one translational energy distribution. The vertical excited energies and the mixed electronic character of excited states were calculated at ab initio configuration interaction method. It is presumed that the high kinetic energy bromine atoms are attributed to the predissociation from 1(pipi*) or 1(pisigma*) state to the repulsive 1(nsigma*) state, and to the direct dissociation from 3(nsigma*) and 3(pisigma*) states, while the low kinetic energy bromine atoms stem from internal conversion from the lowest 3(pipi*) state to 3(pisigma*) state.     

Photodissociation dynamics of CH(2)Br(2) near 234 and 267 nm

The photodissociation dynamics of CH(2)Br(2) was investigated near 234 and 267 nm. A two-dimensional photofragment ion velocity imaging technique coupled with a [2+1] resonance-enhanced multiphoton (REMPI) ionization scheme was utilized to obtain the angular and translational energy distributions of the nascent Br ((2)P(3/2)) and Br* ((2)P(1/2)) atoms. The obtained translational energy distributions of Br and Br* are found consist of two components which should be come from the radical channel and secondary dissociation process, respectively. It is suggested that the symmetry reduction from C(2v) to C(s) during photodissociation invokes a non-adiabatic coupling between the 2B(1) and A(1) states. Consequently, the higher internal energy distribution of Br channel than Br* formation channel and the broader translational energy distribution of the former are presumed correlate with a variety of vibrational excitation disposal at the crossing point resulting from the larger non-adiabatic crossing from 2B(1) to A(1) state than the reverse crossing. Moreover, the measured anisotropy parameter beta indicate that fragments recoil along the Br-Br direction mostly in the photodissociation.     

Photodissociation dynamics of 3-bromo-1,1,1-trifluoro-2-propanol and 2-(bromomethyl) hexafluoro-2-propanol at 234 nm: resonance-enhanced multiphoton ionization detection of Br (2P(j))

The photodissociation dynamics of 3-bromo-1,1,1-trifluoro-2-propanol (BTFP) and 2-(bromomethyl) hexafluoro-2-propanol (BMHFP) have been studied at 234 nm, and the C-Br bond dissociation investigated using resonance-enhanced multiphoton ionization coupled with time-of-flight mass spectrometer (REMPI-TOFMS). Br formation is a primary process and occurs on a repulsive surface involving the C-Br bond of BTFP and BMHFP. Polarization dependent time-of-flight profiles were measured, and the translational energy distributions and recoil anisotropy parameters extracted using forward convolution fits. A strong polarization dependence of time-of-flight profiles suggest anisotropic distributions of the Br((2)P(3/2)) and Br((2)P(1/2)) fragments with anisotropy parameter, β, of respectively 0.5 ± 0.2 and 1.2 ± 0.2 for BTFP, and 0.4 ± 0.1 and 1.0 ± 0.3 for BMHFP. The measured velocity distributions consist of a single velocity component. The average translational energies for the Br((2)P(3/2)) and Br((2)P(1/2)) channels are 9.2 ± 1.0 and 7.4 ± 0.9 kcal/mol for BTFP, and 15.4 ± 1.8 and 15.1 ± 2.0 kcal/mol for BMHFP. The relative quantum yields of Br((2)P(3/2)) and Br((2)P(1/2)), which are 0.70 ± 0.14 and 0.30 ± 0.06 in BTFP and 0.81 ± 0.16 and 0.19 ± 0.04 in BMHFP, indicate that the yield of the former is predominant. The measured anisotropy parameters for the Br((2)P(3/2)) and Br((2)P(1/2)) channels suggest that the former channel has almost equal contributions from both the parallel and the perpendicular transitions, whereas the latter channel has a significant contribution from a parallel transition. Non-adiabatic curve crossing plays an important role in the C-Br bond dissociation of both BTFP and BMHFP. The estimated curve crossing probabilities suggest a greater value in BTFP, which explains a greater observed value of the relative quantum yield of Br((2)P(1/2)) in this case.     

Br(2Pj) atom formation dynamics in ultraviolet photodissociation of tert-butyl bromide and iso-butyl bromide

The photodissociation dynamics of tert-C(4)H(9)Br and iso-C(4)H(9)Br has been studied at 234 and 265 nm using two-dimensional velocity map imaging technique. The translational energy and angular distributions have been analyzed for Br, Br(*), and tert-C(4)H(9) radical. The energy distribution of Br atom in the photodissociation of tert-C(4)H(9)Br is found to consist of two Gaussian components. The two components are correlated to two independent reaction paths on the excited potential energy surfaces: (1) the high-energy component from the prompt dissociation along the C-Br stretching mode and (2) the low-energy component from the repulsive mode along the C-Br stretching, coupled with some bending motions. For the energy distribution of Br(*) atom in the photodissociation of tert-C(4)H(9)Br, a third multiphoton dissociative ionization channel is observed at 265 nm in addition to the two energy components corresponding to channels (1) and (2). The energy distributions of Br and Br(*) atoms in the photodissociation of iso-C(4)H(9)Br can be fitted using only one Gaussian function indicating a single formation channel. Relative quantum yields for Br((2)P(32)) at 234 and 265 nm in the photodissociation of tert-C(4)H(9)Br are measured to be 0.76 and 0.65, respectively. For iso-C(4)H(9)Br, the measured value is Phi(234 nm)(Br)=0.81. The contribution of bending modes to Br and Br(*) is much more obvious in the photodissociation of tert-C(4)H(9)Br than in iso-C(4)H(9)Br.     

溴代烷烃在紫外波段的光解离过程

在飞行时间质谱仪中，采用波长为234 nm和267 nm的激光，研究溴代烷烃CHBr3、CH2Br2、C2H5Br及C2H4Br2的光离解过程.在UV激光的作用下，溴代烷烃分子主要发生的是吸收1个光子解离出Br原子，然后继续吸收光子发生Br原子的（2＋1）共振增强多光子电离的过程.其中由溴代烷烃分子解离得到的Br原子可能存在着两种布居：基态Br(2P03/2)及激发态Br*(2P01/2).研究解离得到的Br原子的分支比 N(Br*)/N(Br)，并给出测量结果：溴代烷烃分子解离得到的Br原子在267 nm激光作用下的分支比明显大于在234 nm激光作用下的结果.对此多光子过程的机理，也进行了分析讨论.     

Photodissociation of 1-bromo-2-butene, 4-bromo-1-butene, and cyclopropylmethyl bromide at 234 nm studied using velocity map imaging

We present photofragment imaging experiments to characterize potential photolytic precursors of three C4H7 radical isomers: 1-methylallyl, cyclopropylmethyl, and 3-buten-1-yl radicals. The experiments use 2+1 resonance enhanced multiphoton ionization (REMPI) with velocity map imaging to state-selectively detect the Br(2P(3/2)) and Br(2P(1/2)) atoms as a function of their recoil velocity imparted upon photodissociation of 1-bromo-2-butene, cyclopropylmethyl bromide, and 4-bromo-1-butene at 234 nm as well as the angular distributions of the photofragments. Energy and momentum conservation allows the internal energy distribution of the nascent momentum-matched radicals to be derived. The radicals are detected with single photon photoionization at 157 nm. In the case of the 1-methylallyl radical the photoionization cross section is expected to be independent of internal energy in the range of 7-30 kcal/mol. Thus, comparison of the product recoil kinetic energy distribution derived from the measurement of the 1-methylallyl velocity distribution, detecting the radicals with 157 nm photoionization, with a linear combination of the Br atom recoil kinetic energy distributions allows us to derive reliable REMPI line strength ratios for the detection of Br atoms and to test the assumption that the photoionization cross section does not strongly depend on the internal energy of the radical. This line strength ratio is then used to determine the branching to the Br(2P(3/2)) and Br(2P(1/2)) product channels for the other two photolytic systems and to determine the internal energy distribution of their momentum-matched radicals. (We also revisit earlier work on the photodissociation of cyclobutyl bromide which detected the Br atoms and momentum-matched cyclobutyl radicals.) This allows us to test whether the 157 nm photoionization of these radicals is insensitive to internal energy for the distribution of total internal (vibrational+rotational) energy produced. We find that 157 nm photoionization of cyclopropylmethyl radicals is relatively insensitive to internal energy, while 3-buten-1-yl radicals show a photoionization cross section that is markedly dependent on internal energy with the lowest internal energy radicals not efficiently detected by photoionization at 157 nm. We present electronic structure calculations of the radicals and their cations to understand the experimental results.     

离子速度成像方法研究溴代环己烷的紫外光解动力学

利用二维离子速度成像方法对C6H11Br分子在234 nm附近的光解动力学行为进行了研究. 通过(2+1)共振增强多光子电离探测了光解产物Br*(2P1/2)和Br(2P3/2), 得到它们的相对量子产率. 从光解产物Br*(2P1/2)和Br(2P3/2)的速度图像得到了能量和角度分布. 结果表明, Br*原子主要来自于S1态的直接解离, 而Br则绝大部分是从S2态向T3态的系间交叉跃迁得到, 并导致了两种解离通道能量分布的差别. 实验发现C6H11Br分子解离过程中大部分能量都转化为内能, 但与其它长链溴代烷烃分子相比, 可资用能更多地被分配到平动能中, 结合软反冲模型分析了这种能量分配跟环烷基的构象和稳定性的关系.     

A photodissociation study of CH2BrCl in the A-band using the time-sliced ion velocity imaging method

Employing a high-resolution (velocity resolution deltanu/nu<1.5%) time-sliced ion velocity imaging apparatus, we have examined the photodissociation of CH2BrCl in the photon energy range of 448.6-618.5 kJ/mol (193.3-266.6 nm). Precise translational and angular distributions for the dominant Br(2P32) and Br(2P12) channels have been determined from the ion images observed for Br(2P32) and Br(2P12). In confirmation with the previous studies, the kinetic-energy distributions for the Br(2P12) channel are found to fit well with one Gaussian function, whereas the kinetic- energy distributions for the Br(2P32) channel exhibit bimodal structures and can be decomposed into a slow and a fast Gaussian component. The observed kinetic-energy distributions are consistent with the conclusion that the formation of the Br(2P32) and Br(2P12) channels takes place on a repulsive potential-energy surface, resulting in a significant fraction (0.40-0.47) of available energy to appear as translational energy for the photo fragments. On the basis of the detailed kinetic-energy distributions and anisotropy parameters obtained in the present study, together with the specific features and relative absorption cross sections of the excited 2A', 1A", 3A', 4A', and 2A" states estimated in previous studies, we have rationalized the dissociation pathways of CH2BrCl in the A-band, leading to the formation of the Br(2P32) and Br(2P12) channels. The analysis of the ion images observed at 235 nm for Cl(2P(32,12)) provides strong evidence that the formation of Cl mainly arises from the secondary photodissociation process CH2Cl + hnu --> CH2 + Cl.     

Br2 molecular elimination in 248 nm photolysis of CHBr2Cl by using cavity ring-down absorption spectroscopy

Elimination of molecular bromine is probed in the B (3)Pi(ou) (+)<--X (1)Sigma(g) (+) transition following photodissociation of CHBr(2)Cl at 248 nm by using cavity ring-down absorption spectroscopy. The quantum yield for the Br(2) elimination reaction is determined to be 0.05+/-0.03. The nascent vibrational population ratio of Br(2)(v=1)Br(2)(v=0) is obtained to be 0.5+/-0.2. A supersonic beam of CHBr(2)Cl is similarly photofragmented and the resulting Br atoms are monitored with a velocity map ion-imaging detection, yielding spatial anisotropy parameters of 1.5 and 1.1 with photolyzing wavelengths of 234 and 267 nm, respectively. The results justify that the excited state promoted by 248 nm should have an A(") symmetry. Nevertheless, when CHBr(2)Cl is prepared in a supersonic molecular beam under a cold temperature, photofragmentation gives no Br(2) detectable in a time-of-flight mass spectrometer. A plausible pathway via internal conversion is proposed with the aid of ab initio potential energy calculations. Temperature dependence measurements lend support to the proposed pathway. The production rates of Br(2) between CHBr(2)Cl and CH(2)Br(2) are also compared to examine the chlorine-substituted effect.     

Multiphoton dissociative ionization of tert-pentyl bromide near 265 nm

We report on the photodissociation dynamics of tert-pentyl bromide near 265 nm investigated by time-sliced velocity map imaging. The speed and angular distributions have been analyzed for both the ground-state Br((2)P(3∕2)) atom (denoted Br) and the spin-orbit excited-state Br((2)P(1∕2)) atom (denoted Br*). The speed distributions of Br and Br* atoms are all found to consist of three Gaussian components, which correlate to three independent dissociation pathways on the excited potential energy surfaces: (1) the high translational energy (E(T)) component from the prompt dissociation along the C-Br stretching mode, (2) the middle E(T) component from the repulsive mode along the C-Br stretching coupled with some bending motions, and (3) the low E(T) component from the repulsive mode along the C-Br stretching coupled with more bending motions. More interestingly, we have also observed the tert-C(5)H(11)(+) ions in 263-267 nm. The near-zero kinetic energy distributions extracted from the three tert-C(5)H(11)(+) images near 265 nm show the typical characteristics that are attributable to multiphoton dissociative ionization, suggesting the existence of a neutral superexcited state of the parent tert-pentyl bromide molecule. The contribution of bromine atoms formed in this dissociative ionization channel adds in the total relative distribution of low E(T) component in the Br*(Br) formation channel, which reasonably explains the abnormal distributions observed in between the middle and low E(T) components in the Br*(Br) formation channel.     

Laser-induced UV photodissociation of 2-bromo-2-nitropropane: dynamics of OH and Br formation

Photoexcitation of 2-bromo-2-nitropropane (BNP) at 248 and 193 nm generates OH, Br, and NO(2) among other products. The OH fragment is detected by laser-induced fluorescence spectroscopy, and its translational and internal state distributions (vibration, rotation, spin-orbit, and Λ-doubling components) are probed. At both 248 and 193 nm, the OH fragment is produced translationally hot with the energy of 10.8 and 17.2 kcal∕mol, respectively. It is produced vibrationally cold (v" = 0) at 248 nm, and excited (v" = 1) at 193 nm with a vibrational temperature of 1870 ± 150 K. It is also generated with rotational excitation, rotational populations of OH(v" = 0) being characterized by a temperature of 550 ± 50 and 925 ± 100 K at 248 and 193 nm excitation of BNP, respectively. The spin-orbit components of OH(X(2)Π) are not in equilibrium on excitation at 193 nm, but the Λ-doublets are almost in equilibrium, implying no preference for its π lobe with respect to the plane of rotation. The NO(2) product is produced electronically excited, as detected by measuring UV-visible fluorescence, at 193 nm and mostly in the ground electronic state at 248 nm. The Br product is detected employing resonance-enhanced multiphoton ionization with time-of-flight mass spectrometer for better understanding of the dynamics of dissociation. The forward convolution analysis of the experimental data has provided translational energy distributions and anisotropy parameters for both Br((2)P(3∕2)) and Br?((2)P(1∕2)). The average translational energies for the Br and Br? channels are 5.0 ± 1.0 and 6.0 ± 1.5 kcal∕mol. No recoil anisotropies were observed for these products. Most plausible mechanisms of OH and Br formation are discussed based on both the experimental and the theoretical results. Results suggest that the electronically excited BNP molecules at 248 and 234 nm relax to the ground state, and subsequently dissociate to produce OH and Br through different channels. The mechanism of OH formation from BNP on excitation at 193 nm is also discussed.     

Photodissociation of 2-Bromobutane at ～265 nm by Ion-velocity Map Imaging Technique

The photodissociation dynamics of 2-bromobutane has been investigated at 264.77 and 264.86 nm by ion-velocity map imaging technique coupled with resonance-enhanced multi-photon ionization. The speed and angular distributions have been derived from the velocity map images of Br and Br*. The speed distributions of Br and Br* atoms in the photodis-sociation of 2-bromobutane at ～265 nm can be fitted using only one Gaussian function indicating that bromine fragments were produced via direct dissociation of C-Br bond. Thecontributions of the excited ³Q₀, ³Q₁, and ¹Q₁ states to the products (Br and Br*) were discussed. It is found that the nonadiabatic ¹Q₁←³Q₀ transition plays an important role for Br photofragment in the dissociation of 2-C₄H₉Br at ～265 nm. Relative quantum yield of 0.621 for Br(²P_3/2) at ～265 nm in the photodissociation of 2-bromobutane is derived. By comparing the photodissociation of 2-C₄H₉Br at ～265 nm and that that at ～234 nm, the anisotropy parameter β(Br) and β(Br*), and relative quantum yield ?(Br) decrease with increasing wavelength, the probability of curve crossing between ³Q₀ and ¹Q₁ decreases with increasing laser wavelength.     

Imaging CIN(3) photodissociation from 234 to 280 nm

We report Cl((2)P(3/2)) and Cl*((2)P(1/2)) fragment images following ClN(3) photolysis in the 234-280 nm region measured by velocity map imaging. Kinetic energy distributions change shape with photolysis wavelength from bimodal at 234 and 240 nm to single peak at 266 and 280 nm. Where two peaks exist, their ratio is significantly different for Cl and Cl* fragments. The single peak of 266 and 280 nm and the faster peak at 234 and 240 nm are assigned to a Cl + linear-N(3) dissociation channel, in agreement with previous work. The slow peak in the bimodal distributions is assigned to the formation of a high energy form (HEF) of N(3). Candidates for the identity of HEF-N(3) are discussed. Combining our data with photofragmentation translational spectroscopy results, we determined the threshold for the appearance of HEF-N(3) at 4.83 +/- 0.17 eV photolysis energy. This threshold behavior is similar to recently reported results on the wavelength dependence of HN(3) photolysis, where the threshold was associated with a ring closed isomer of HN(3) on the S(1) potential energy surface. We also note that the HEF-N(3) formation threshold observed for ClN(3) occurs where the energy available to the products equals the isomerization barrier from linear to cyclic-N(3).     

Photodissociation of 2-Bromobutane by Ion-velocity Map ImagingTechnique

The photodissociation dynamics of 2-bromobutane has been investigated at 233.62 and 233.95 nm by ion-velocity map imaging technique coupled with resonance-enhanced mul-tiphoton ionization. The speed and angular distribution of Br and Br* fragments were determined from the map images. The two Gaussian components, shown in the speed dis-tributions of Br and Br* atoms, are suggested to attribute to the two independent reaction paths of photodissociation for 2-bromobutane at 233.62 and 233.95 nm. The high-energy component is related to the prompt dissociation along the C-Br stretching mode, and the low-energy component to the dissociation from the repulsive mode with bending and C-Br stretching combination. The contributions of the excited ³Q₀, ³Q₁, and ¹Q₁ states to the products (Br and Br*) were discussed. Relative quantum yield of 0.924 for Br(²P_3/2) at about 234 nm in the photodissociation of 2-bromobutane is derived.