Highly selective population of two excited states in nonresonant two-photon absorption

A nonresonant two-photon absorption process can be manipulated by tailoring the ultra-short laser pulse.In this paper,we theoretically demonstrate a highly selective population of two excited states in the nonresonant two-photon absorption process by rationally designing a spectral phase distribution.Our results show that one excited state is maximally populated while the other state population is widely tunable from zero to the maximum value.We believe that the theoretical results may play an important role in the selective population of a more complex nonlinear process comprising nonresonant two-photon absorption,such as resonance-mediated (2+1)-three-photon absorption and (2+1)-resonant multiphoton ionization.     

Theory of coherent,degenerate two-photon absorption and emission

The theory of the coherent, two-photon resonant interaction of a monochromatic field with N atoms is given. It is seen that the dynamics of the atom-field system can be completely determined when the field is “strong”. Two specific examples are given: (i) two-photon absorption by atoms in ground state, and (ii) stimulated two-photon emission by fully excited atoms, assuming a coherent field in both cases. In case (ii), the field shows photon-antibunching after the decay of half of the atoms. The merits of our approach are shown by comparing with other treatments. Our results can also be applied to certain degenerate four-wave mixing processes which are described by a similar Hamiltonian.     

One- and two-photon absorption properties of two metalloporphyrin complexes

The linear and nonlinear optical properties of two metalloporphyrin complexes formed by the complementary coordination of central zinc or magnesium ions to the ligand 5, 10, 15-tri-(p-tolyl)-20-phenylethynylporphyrin are theoretically investigated by using the analytic response theory at the density functional theory level. The results indicate that the studied complexes present more symmetric geometry structures than the ligand. The charge-transfer states of the two complexes in the lower energy region are all almost degenerate but those of the ligand are well separated. The ratio of the two-photon absorption cross sections of the ligand, zinc-porphyrin and magnesium-porphyrin complexes is 1.0:1.5:1.8, demonstrating that the two-photon absorption capability can be greatly increased when the ligand is coordinated with a metal ion. Moreover, several physical micro-mechanisms including electron transitions and intramolecular charge-transfer processes are discussed to explore the differences in optical property between the ligand and two complexes.     

有机染料HEASPS在不同波长时的激发态吸收和双光子吸收性质研究

提出了有机染料反式 4 [4′ (N 羟乙基 N 乙基胺基 )苯乙烯基 ] N 甲基吡啶对甲苯磺酸盐 (简称HEASPS)非线性吸收的三态模型。认为在较短波长 (<1 0 0 0nm)时 ,双光子吸收和激发态吸收同时存在。成功地解释了该染料双光子吸收峰相对线性吸收峰的两倍的明显蓝移 ,以及最高上转换效率波长相对最强吸收波长的明显红移。提出了一种新的计算方法 ,利用不同波长的非线性透过率和不同波长的上转换效率 ,求出了该染料的双光子吸收截面和激发态吸收系数。     

双光子吸收的Franz-Keldysh效应

从实验上证实Hg_0.695Cd_0.305Te 光电二极管空间电荷区中存在双光子吸收的Franz-Keldysh效应.利用一个皮秒Nd:YAG激光器抽运的光学参量产生器和差频产生器作为激发光源，测量了入射波长为λ₀=7.92μm的脉冲激光所激发的光响应随入射光强的变化关系.脉冲光响应峰值强度随入射光强的增大呈现二次幂函数增强趋势.采用等效RC电路模型将脉冲光伏信号峰值与入射光强相关联，得到空间电荷区中强电场下单光束     

双光子吸收的Franz-Keldysh效应

从实验上证实Hg_0.695Cd_0.305Te 光电二极管空间电荷区中存在双光子吸收的Franz-Keldysh效应.利用一个皮秒Nd:YAG激光器抽运的光学参量产生器和差频产生器作为激发光源,测量了入射波长为λ₀=7.92μm的脉冲激光所激发的光响应随入射光强的变化关系.脉冲光响应峰值强度随入射光强的增大呈现二次幂函数增强趋势.采用等效RC电路模型将脉冲光伏信号峰值与入射光强相关联,得到空间电荷区中强电场下单光束 关键词： Franz-Keldysh效应 碲镉汞 双光子吸收 脉冲光伏信号     

The theoretical studies on the two-photon absorption properties of symmetric 1,4-bis{2-[4-（2- aryl） phenyl] vinyl }- 2,5-bisdialkoxyb enzenes

On the level of the time-dependent hybrid density functional theory, the one- and two-photon absorption properties of a series of symmetric 4-bis 2-[4-(2-ary12) phenyl]vinyl-2,5-bisdialkoxybenzenes are studied respectively utilizing the analytic response theory and the few-state model methods. The calculated results show that the planarity of the geometrical structure plays a great role in enhancing the linear and nonlinear optical abilities of the molecule. However the effect of the length of the chain linked to the π-centre on the optical property is very little. For the investigated compounds, the A–π–A type charge-transfer molecules display more superior one- and two-photon absorption characteristics than the D–π–D type ones. Furthermore, the two-photon absorption results by use of few-state model are generally consistent with those by analytic response theory, demonstrating the reliability of the few-state model for evaluating the two-photon absorption cross section. The numerical simulations are in good agreement in tendency with the available experimental measurements.     

Coherent control of non-resonant two-photon transition in molecular system

In this paper,we study theoretically and experimentally the coherent control of non-resonant two-photon transition in a molecular system (Perylene dissolved in chloroform solution) by shaping the femtosecond pulses with simple phase patterns (cosinusoidal and π phase step-function shape).The control efficiency of the two-photon transition probability is correlated with both the laser field and the molecular absorption bandwidth.Our results demonstrate that,the two-photon transition probability in a molecular system can be reduced but not completely eliminated by manipulating the laser field,and the control efficiency is minimal when the molecular absorption bandwidth is larger than twice the laser spectral bandwidth.     

Quantum coherent control of two-photon transitions by square phase-modulation

A femtosecond laser pulse can be tailored to control the two-photon transitions using the ultra-fast pulse-shaping technique. This paper theoretically and experimentally demonstrates that two-photon transitions in molecular system with broad absorption line can be effectively controlled by square phase-modulation in frequency domain, and the influence of all parameters characterizing the square phase-modulation on two-photon transitions is systemically investigated and discussed. The obtained results have potential application in nonlinear spectroscopy and molecular physics.     

Laser photoacoustic spectroscopy of iodine molecule: Single and two-photon absorption

Photoacoustic spectroscopy of iodine molecule has been studied in gas phase using nitrogen laser-pumped tunable dye laser. The experiment yielded the vibrational spectrum corresponding toX ¹Σ⁺(0 _g ⁺ )→B ³Π(0 _g ⁺ ) transition up to the convergence limit. The photo-acoustic spectrum in the region 17580–18850 cm⁻¹ is presented along with the vibrational analysis. Five of the vibrational bands reported earlier by Venkateswarlu, Kumar and McGlynn have been partially resolved and the structure of one of them has been analyzed and shown to be due to an overlap of (14, 2) and (12, 1) bands. The analysis was based on a comparison with the highly resolved spectrum of Gerstenkorn and Luc. The structure observed in the region 20200–20750 cm⁻¹ which is beyond the convergence limit of the transitionX ¹Σ⁺(0 _g ⁺ )→B ³Π(0 _u ⁺ ) has been analyzed as due to two-photon absorption. Most of the bands could be assigned to two transitions both originating in the ground state and terminating in two different electronic states 1 _g andE(0 _g ⁺ ), atT _e=40821 cm⁻¹ (orT ₀=41355 cm⁻¹) andT _e=41411 cm⁻¹ (orT ₀=41355 cm⁻¹) respectively.     

Influence of rotational isomerism on two-photon absorption properties of FTC chromophores

The influence of rotational isomerism on the two-photon absorption(TPA) of FTC chromophores has been investigated using the quadratic response theory with the B3LYP functional.Eight rotamers induced by three rotatable single bonds in the molecule are fully optimized,and it is found that their conformational energies are nearly degenerate.Our calculations demonstrate that rotational isomerism has an important effect on the TPA cross sections.For a certain rotamer,the maximum TPA cross section is enhanced significantly.In addition,in the longer wavelength region,the rotational isomerism could lead to a large shift of the TPA position.     

Theoretical studies on the one- and two-photon absorption properties of azulenylporphyrins and azulene-fused porphyrins

The electronic structures, one-photon absorption (OPA) and two-photon absorption (TPA) properties of the azulenylporphyrins and azulene-fused porphyrins have been comparatively studied by using DFT/B3LYP/6-31G(d) and the ZINDO/SDCI method. With the number of azulenyl groups increasing, the OPA wavelengths of all molecules are red-shifted in 400--600~nm and the two-photon absorption cross section is gradually enlarged. The azulene-fused structures facilitate an expanding conjugated area and increasing TPA cross section. The origin of TPA properties of studied compounds is studied with a two-level model. In summary, the azulene-fused porphyrins exhibit strong two-photon absorption.     

Polarization and phase control of two-photon absorption in an isotropic molecular system

<正>We theoretically and experimentally study the polarization and phase control of two-photon absorption in an isotropic molecular system.We theoretically show that the two-photon transition probability decreases when the laser polarization changes from linear through elliptical to circular,and the laser polarization does not affect the control efficiency of two-photon transition probability by shaping the spectral phase.These theoretical results are experimentally confirmed in coumarin 480.Furthermore,we propose that the combination of the laser polarization with the spectral phase modulation can further increase the control efficiency of the two-photon absorption.     

Qauntum theory of two-photon absorption in a driven F-P cavity with the feedback of photon flux

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Effect of side groups on two-photon absorption of soluble polythiophenes

The effect of pendant side groups on two-photon absorption cross-section in a number of soluble fluorescent polythiophenes was investigated. Different side groups lead to different planarity and conformation of the polymer. As the side-group-induced planarity of the polymer chain increases, the two-photon absorption cross-section also increases. The increased delocalization of the π-electrons along the polymer backbone enhances the third-order optical nonlinearity. The aggregation of the polymer chain in solution lowers the quantum efficiency of fluorescence and decreases the two-photon absorption cross-section. This study demonstrates a novel method of enhancing the two-photon absorption cross-section by tuning the pendant side group.     

新型多共轭链有机分子双光子吸收特性的理论研究

在密度泛函理论水平上,利用解析响应函数方法研究了以（4-{2-［4-（2-吡啶-4-乙烯基）-苯基］-乙烯基}-苯基）-胺为基本结构单元的单支、双支和三支共轭链有机分子的单光子和双光子吸收特性.计算结果表明,这三种有机分子都具有较大的线性和非线性吸收强度.在紫外-可见光区域,它们的单光子吸收谱都存在两个峰,这与实验结果符合较好.在近红外区域,多共轭链有机分子呈现出宽达300 nm的宽带双光子吸收,单支、双支和三支分子的最大双光子吸收截面比约为1.0∶2.3∶4.0,其中三支分子具有最大的双光子吸收截面101.73×10^-48 cm⁴·s.从理论上进一步证实,增加分子的共轭链可有效提高分子的双光子吸收特性.同时还给出了电荷转移态的电荷迁移过程. 关键词： 双光子吸收 响应函数方法 多共轭链有机分子     

1，4-二甲氧基-2，5-二乙烯基苯系列衍生物的双光子吸收截面

在HF水平上，利用解析响应函数方法，研究了1，4_二甲氧基_2，5_二乙烯基苯系列衍生物 分子的单光子和双光子吸收特性. 实验测量了反，反_2，5_双(4′_N,N_二丁胺基苯乙烯)_1 ，4_二甲氧基苯分子的单光子和双光子荧光谱. 研究结果表明该系列分子具有较强的双光子 吸收特性. 在低能量范围内，对于D_π-A型分子，分子的单光子吸收强度和双光子吸收截面 最大值都发生在分子的第一激发态. 对于D_π_D型分子，单光子吸收强度最大值出现在分子 的第一激发态，而最大双光子吸收值则对应于分子的第二激发态. 分子的单和双光子吸收强 度和分子官能团的电性有关. 对于由该类π中心部分构成的分子，其对称型不一定比不对称型更有利于提高双光子吸收截面. 分子基态与电荷转移态的电荷转移过程定性地解释了双光 子聚合反应的聚合机理. 关键词： 双光子吸收 响应函数方法 非线性光学     

(E,E)-1,4-双{2''-[5''-(B,B-二甲基苯硼)-2-噻吩基]乙烯基}-苯分子双光子吸收特性的理论研究

在密度泛函水平上,利用响应函数方法,研究了分子的单光子和双光子吸收特性.计算出了该分子在低能量范围内的最大双光子吸收截面为6.47×10-47cm4s/photon,与实验符合的较好.研究结果表明该分子具有较强的双光子吸收特性,是较好的双光子吸收材料.     

双光子吸收材料用于高功率激光近场控制技术

 为了提高高功率激光光束质量和改善近场均匀性,在SILEX-Ⅰ超短脉冲激光装置的泵浦光系统上进行实验,研究了一种双光子吸收材料的光限幅特性及对激光近场的改善情况。利用泵浦光SAGA激光器输出的激光进行光限幅特性实验。结果表明:该材料具有明显的光功率限幅特性,且透过率较高,当入射光强小于0.60 GW/cm₂时,透过率大于90%。在SILEX-Ⅰ装置的泵浦光系统进行联机实验,研究了该材料对激光近场均匀性的改善。实验结果表明:经过材料后,激光近场均匀性和调制度有明显改善。     

Y型四能级系统中Doppler展宽对VIC相关的双光子吸收的影响

利用数值计算结果讨论了Doppler展宽对Y型四能级原子系统中真空诱导相干 性(VIC)相关的双光子吸收的影响. 研究结果表明: 1)在无Doppler展宽的情况中, 不存在VIC时, 吸收曲线具有双峰结构并产生电磁感应透明(EIT)现象, 存在VIC时吸收曲线具有单峰结构而EIT现象不再发生; 2)在有Doppler展宽的情况中, 不管是否存在VIC, EIT现象都能发生; 不存在VIC时, 不管探测场和驱动场传播方向相同还是相反, 随Doppler展宽宽度D值的增大, 吸收先增大后减小, 吸收曲线逐渐从双峰结构变为单峰结构; 存在VIC时, 若探测场和驱动场传播方向相同, 随D值的增大, 吸收先增大后减小, 吸收曲线逐渐从单峰结构变为双峰结构; 若探测场和驱动场传播方向相反, 随D值的增大, 吸收单调减小, 但吸收曲线仍保持单峰结构.