scholarly journals Density Functional Theory Predictions of the Nonlinear Optical (NLO) Properties in Triphenylamine based α-Cyanocinnamic Acid Compounds: Effect of Fluorine on NLO Response

2019 ◽  
Vol 62 (3) ◽  
Author(s):  
Muhammad Ramzan Saeed Ashraf Janjua Janjua
Keyword(s):  
Phenyl Ring ◽  
Density Functional ◽  
Nonlinear Optical ◽  
Second Order ◽  
Functional Theory ◽  
Nlo Properties ◽  
Nlo Response ◽  
Nlo Materials ◽  
Cyanocinnamic Acid ◽  
Insight Into

In this study, the energy gaps, second-order nonlinear optical (NLO) properties and dipole polarizabilities of triphenylamine based α-cyanocinnamic acid acetylene derivatives have been investigated via using time-dependent density functional response theory. These compounds were designed theoretically by fluorine (F) atom substitution at different positions of phenyl ring end of the α-cyanocinnamic acid segment. The results have indicated that the systems substituted by fluorine show remarkable NLO second-order response, especially D4 system with computed static second-order polarizability (βtot) of 70537.95 (a.u). Hence, these materials have the likelihood to be an excellent second-order nonlinear optical (NLO) materials. The βtot value suggests that along the x-axis the charge transfer (CT) from triphenylamine to α-cyanocinnamic acid (D-A) plays a key role in NLO response; whereas α-cyanocinnamic acid acts as an acceptor (A) and triphenylamine acts as a donor (D) in all the studied systems. Incorporation of an electron acceptor (F) at the phenyl ring end of the α-cyanocinnamic acid segment increases the computed βtot values. The present investigation therefore provides an important insight into the remarkably greater NLO properties of α-cyanocinnamic acid and triphenylamine attached via acetylene.

Tuning Second-Order Non-linear (NLO) Optical Response of Organoimido-Substituted Hexamolybdates through Halogens: Quantum Design of Novel Organic-Inorganic Hybrid NLO Materials

2010 ◽  
Vol 63 (5) ◽  
pp. 836 ◽  
Author(s):  
Muhammad Ramzan Saeed Ashraf Janjua ◽  
Zhong-Min Su ◽  
Wei Guan ◽  
Chun-Guang Liu ◽  
Li-Kai Yan ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Phenyl Ring ◽  
Density Functional ◽  
Organic Ligand ◽  
Second Order ◽  
Inorganic Hybrid ◽  
Nlo Properties ◽  
Nlo Response ◽  
Non Linear ◽  
Nlo Materials

The second-order non-linear optical (NLO) response of organoimido-substituted hexamolybdates has been tuned from 218.61 × 10–30 to 490.10 × 10–30 esu. The dipole polarizabilities and second-order nonlinear optical (NLO) properties of organoimido derivatives of hexamolybdates have been investigated by using the time-dependent density functional response theory (TDDFT). The electron withdrawing ability of F (fluorine) has played an important role in tuning the second-order NLO response in this class of organic-inorganic hybrid compounds; particularly system 6 [Mo6O18(NC16H8F2(CF3)2I)]2– with the static second-order polarizability (βvec ) computed to be 490.10 × 10–30 esu. Thus, our studied systems have the feasibility to be excellent tuneable second-order NLO materials. The analysis of the major contributions to the βvec value suggests that the charge transfer (CT) from POM to organic ligand (D-A) along the z-axis has been enhanced with addition of F atoms at the end phenyl ring which directs head (POM) to tail (fluorinated ring) charge transfer. The computed βvec values have been tuned by incorporation of different halogen atoms at the end phenyl ring of organoimido segment. Furthermore, substitution of two trifluoromethyl (–CF3) groups sideways along with iodine (I) at the terminus of end phenyl ring in the organoimido ligand has a striking influence on tuning the optical non-linearity, as CT from POM to the organoimido ligand was significantly increased. These systematic small changes in molecular composition by substitution of different halogen groups leads to a tuning the NLO response; the so-called ‘ripple effect’ catches this point nicely. Thus, the present investigation provides thought provoking insight into the tuneable NLO properties of organoimido-substituted hexamolybdates.

Theoretical exploration to the cation effect on the second-order nonlinear optical properties of Strandberg-type polyoxometalates

2015 ◽  
Vol 14 (01) ◽  
pp. 1550007 ◽  
Author(s):  
Ting Zhang ◽  
Wei Guan ◽  
Shizheng Wen ◽  
Tengying Ma ◽  
Likai Yan ◽  
...  
Keyword(s):  
Density Functional ◽  
Nonlinear Optical ◽  
Dft Method ◽  
Transition Metal Ions ◽  
Second Order ◽  
Functional Theory ◽  
Cation Effect ◽  
Nlo Response ◽  
Polar Materials ◽  
Nlo Materials

The combination of cations with octahedral coordinated d0 transition metal ions has been proved to be an effective way for designing new polar materials. So we investigate the second-order nonlinear optical (NLO) properties of Strandberg-type polyoxometalates (POMs) with alkali metal cations M 6 Mo 5 X 2 O 23 ( M = K +, Rb +, Cs +; X = P , As ) and M 4 M o5 X 2 O 21 ( M = K +, Rb +, Cs +; X = S , Se , Te ) by density functional theory (DFT) method. The calculated results show that this kind of Strandberg-type POMs possesses remarkably large molecular second-order NLO polarizability, especially for the Cs 6 Mo 5 P 2 O 23 (system Ic), which has a computed β0 value of 12526 a.u. and might be an excellent second-order NLO material. Moreover, the cations have important impact on the second-order NLO polarizabilities. Therefore, a careful choice of appropriate cations may allow the control of the second-order NLO response on these Strandberg-type POMs, which may provide a new route to design efficient NLO materials.

A Theoretical Investigation on Second-Order NLO Properties of Organic Substitutions of [Mo6O19]2- and [MoW5O19]2-

2019 ◽  
Vol 960 ◽  
pp. 268-273
Author(s):  
Qi Li ◽  
Xiu Hua Yuan
Keyword(s):  
Molecular Structure ◽  
High Performance ◽  
Density Functional ◽  
Nonlinear Optical ◽  
Second Order ◽  
Functional Theory ◽  
Nlo Properties ◽  
Potential Applications ◽  
Nlo Materials ◽  
Different Parts

In this study, density functional theory (DFT) was used to calculate second-order polarizabilities and second-order polarizabilities densities of a series of organic substitution for Lindqvist-type polyoxometalates (POMs), and the nonlinear optical (NLO) properties was also analyzed. We found that βzzz has the main contribution to β value. The expansion of molecular structure on z-axis greatly increased second-order polarizabilities. Both the size of the organic segments and metal hybridization exert an influence on β value. The analysis on the second-order polarizabilities density is used to explain the NLO phenomenon. In the present investigation, metal hybridization and π-conjugation changed the contribution of βzzz value from different parts. The results of this work will contribute to the potential applications in high-performance NLO materials.

THEORETICAL STUDY ON THE SECOND-ORDER NONLINEAR OPTICAL PROPERTIES OF C,B-SUBSTITUTED CARBORANE CONJUGATED DERIVATIVES

2012 ◽  
Vol 11 (05) ◽  
pp. 1121-1133 ◽  
Author(s):  
YAN LIU ◽  
GUOCHUN YANG ◽  
SHILING SUN ◽  
FEI YU ◽  
ZHONGMIN SU ◽  
...  
Keyword(s):  
Density Functional ◽  
Nonlinear Optical ◽  
Transition Energy ◽  
Energy Transition ◽  
Second Order ◽  
Orbital Energy ◽  
First Hyperpolarizability ◽  
Structure Property ◽  
Functional Theory ◽  
Nlo Materials

To systemically investigate structure–property relationship and design excellent nonlinear optical (NLO) material, the second-order NLO properties of a series of C,B -substituted carborane conjugated derivatives have been studied by density functional theory (DFT). The static first hyperpolarizabilities (βtot) were calculated at the M05-2X/6-31+G* level of theory. The results show that the βtot values gradually increase with the increasing of the conjugation length, especially the introduction of ferrocene. It is found that 1,3-benzo-o-carborane-ferrocene (2h) has the largest first hyperpolarizability (55.968 × 10-30 esu), which is 150 times larger than that of benzocarborane (1a). This means that the static first hyperpolarizabilities of the studied compounds can be substantially increased by structural modification. A basis for understanding the origin of these large NLO responses is proposed based on consideration of the frontier molecular orbitals (FMOs), orbital energy, transition energy of the studied compounds, and the two-state mode. The lower transition energy and larger oscillator strength play an important role in increasing the first hyperpolarizability value. This study may evoke possible ways to design preferable NLO materials.

Switchable second-order nonlinear optical response of platinum-sensitized dithienylethenes

2019 ◽  
Vol 18 (04) ◽  
pp. 1950022
Author(s):  
Xiao-Yun Liu ◽  
Zhi-Yuan Shi ◽  
Jin-Ting Ye ◽  
Hui-Ying Wang ◽  
Hong-Qiang Wang ◽  
...  
Keyword(s):  
Density Functional ◽  
Nonlinear Optical ◽  
Dft Method ◽  
Second Order ◽  
Computational Formula ◽  
Functional Theory ◽  
Nlo Properties ◽  
Closed Ring ◽  
The Density Functional Theory ◽  
Ring Complexes

The electronic structure and the nonlinear optical (NLO) properties of a series of platinum-sensitized dithienylethenes (DTEs) were investigated by using the density functional theory (DFT) method. DFT calculations reveal that the second-order NLO properties of complexes significantly increase with the DTE ligand being directly linked with terpyridine–Pt(II) complexes. Due to the good [Formula: see text]-conjugated characteristics, closed-ring complexes possess much larger second-order NLO properties than the corresponding open-ring complexes. The computational [Formula: see text] values are in the order of 3c ([Formula: see text] esu) [Formula: see text] 3o ([Formula: see text] esu) [Formula: see text] 4c ([Formula: see text] esu) [Formula: see text] 4o ([Formula: see text] esu) [Formula: see text] 1 ([Formula: see text] esu) [Formula: see text] 2c ([Formula: see text] esu) [Formula: see text] 2o ([Formula: see text] esu). Among all calculated platinum-sensitized dithienylethenes, 3c has the largest second-order NLO properties. The 4c and 4o have almost the same [Formula: see text] values and the [Formula: see text] value of 4o is slightly larger than that of 2o because the ether bonds can significantly prevent charge transfer within the complexes.

THE INVESTIGATION ON ELECTRONIC STRUCTURE AND SECOND-ORDER NONLINEAR OPTICAL PROPERTIES OF II–VI SEMICONDUCTOR CLUSTERS BY TIME-DEPENDENT DENSITY FUNCTIONAL THEORY

2007 ◽  
Vol 06 (03) ◽  
pp. 585-594 ◽  
Author(s):  
YONGQING QIU ◽  
XIAOHONG WANG ◽  
YICHUN LIU ◽  
GUOCHUN YANG ◽  
HUI CHEN
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Nonlinear Optical ◽  
Second Order ◽  
Time Dependent ◽  
Basis Sets ◽  
Functional Theory ◽  
Nlo Properties ◽  
Semiconductor Clusters ◽  
Dependent Density

Time-dependent density functional theory (TD-DFT) formalism is employed to calculate the electronic spectra of A 3 B 3 II–VI semiconductor clusters based on the geometrical structures optimized at DFT-B3LYP level. Moreover, their second-order nonlinear optical (NLO) properties are performed by TD-B3LYP combined with sum-over-states (SOS) formula. The calculation results indicate that it is necessary to consider the effective core potential and electron correlation effects when the basis sets are chosen for the heavy atoms. In addition, the results show that the transition energies and HOMO–LUMO gaps of the A 3 B 3 II–VI semiconductor clusters decrease, while the second-order nonlinear optical responses increase with the increasing of VI-group ionic radius. As a result, the SOS formula is valuable to calculate the βμ in the summation of 120 states. Meanwhile, charge transfers from the π bonding to π anti-bonding orbitals between II and VI group atoms significantly contribute to the second-order NLO properties.

scholarly journals Structural modulation of π-conjugated linkers in D–π–A dyes based on triphenylamine dicyanovinylene framework to explore the NLO properties

2021 ◽  
Vol 8 (8) ◽  
pp. 210570
Author(s):  
Muhammad Khalid ◽  
Muhammad Usman Khan ◽  
Iqra Shafiq ◽  
Riaz Hussain ◽  
Akbar Ali ◽  
...  
Keyword(s):  
Absorption Spectra ◽  
Optical Materials ◽  
Density Functional ◽  
Visible Region ◽  
Functional Theory ◽  
Nlo Properties ◽  
Structural Modifications ◽  
Nlo Response ◽  
Nlo Materials ◽  
Structural Modulation

A donor–π–acceptor type series of Triphenylamine–dicyanovinylene-based chromophores ( DPMN1–DPMN11 ) was designed theoretically by the structural tailoring of π-linkers of experimentally synthesized molecules DTTh and DTTz to exploit changes in the optical properties and their nonlinear optical materials (NLO) behaviour. Density functional theory (DFT) computations were employed to understand the electronic structures, absorption spectra, charge transfer phenomena and the influence of these structural modifications on NLO properties. Interestingly, all investigated chromophores exhibited lower band gap (2.22–2.60 eV) with broad absorption spectra in the visible region, reflecting the remarkable NLO response. Furthermore, natural bond orbital (NBO) findings revealed a strong push–pull mechanism in DPMN1–DPMN11 as donor and π-conjugates exhibited positive, while all acceptors showed negative values. Examination of electronic transitions from donor to acceptor moieties via π-conjugated linkers revealed greater linear (〈 α 〉 = 526.536–641.756 a.u.) and nonlinear ( β tot = 51 313.8–314 412.661 a.u.) response. It was noted that the chromophores containing imidazole in the second p-linker expressed greater hyperpolarizability when compared with the ones containing pyrrole. This study reveals that by controlling the type of π-spacers, interesting metal-free NLO materials can be designed, which can be valuable for the hi-tech NLO applications.

Theoretical investigation of second-order nonlinear optical response — Hexamolybdate as a superior donor over metal carbonyl complexes in the D–π–A model

2011 ◽  
Vol 89 (1) ◽  
pp. 61-67 ◽  
Author(s):  
Ping Song ◽  
Chunguang Liu ◽  
Wei Guan ◽  
Likai Yan ◽  
Xiaolei Sun ◽  
...  
Keyword(s):  
Density Functional ◽  
Nonlinear Optical ◽  
Metal Carbonyl ◽  
Electron Transition ◽  
Carbonyl Complexes ◽  
Metal Carbonyl Complexes ◽  
Nlo Response ◽  
Nlo Materials ◽  
Transition Channel ◽  
Donor Moiety

Density functional theory (DFT) calculations were carried out to investigate the nonlinear optical (NLO) response for the donor-conjugated bridge-accepter (D–π–A) model of p-nitroaniline (PNA) – hexamolybdate derivatives and PNA–metal–carbonyl complexes. The bond length alternation (BLA) values decrease with lengthening of the π-conjugated bridge, especially for PNA–hexamolybdate derivatives, which dramatically enhances the NLO response. In addition, the introduction of Mo≡N in PNA–hexamolybdate derivatives is expected to provide a better electron transition channel, consequently generating lower BLA values and an outstanding NLO response compared with PNA–metal–carbonyl complexes. It is shown that the hexamolybdate acts as an electron donor when incorporating metal–carbonyl complexes into one molecule. All these behaviors reflect the superiority of hexamolybdate as a donor moiety in the D–π–A model for the design of potential NLO materials.

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