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RESEARCH PAPER · Journal of the American Chemical Society · 2016

Designing a Beryllium-Free Deep-Ultraviolet Nonlinear Optical Material without a Structural Instability Problem

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Designing a Beryllium-Free Deep-Ultraviolet Nonlinear Optical Material without a Structural Instability ProblemOriginalNonlinear optical response mechanism of noncentrosymmetric lead borate Pb 6 [B 4 O 7 (OH) 2 ] 3 with three crystallographically independent [B 4 O 7 (OH) 2 ] 4− chains8Pb 2 Bi 2 GaB 3 O 11 , a new congruent-melting galloborate containing two types of asymmetric cations with a moderate birefringence5Top-Seeded Solution Crystal Growth, Morphology, Optical and Thermal Properties of Ba3(ZnB5O10)PO442ChemInform Abstract: Designing a Beryllium‐Free Deep‐Ultraviolet Nonlinear Optical Material Without a Structural Instability Problem.0Crystal Growth and Associated Properties of a Nonlinear Optical Crystal—Ba2Zn(BO3)226A New Deep-Ultraviolet Transparent Orthophosphate LiCs 2 PO 4 with Large Second Harmonic Generation Response384Titanosilicates with Strong Phase-Matched Second Harmonic Generation Responses77DFT Based Theoretical Study about the Contributions of Fluorine to Nonlinear Optical Properties in Borate Fluoride Crystals27Syntheses, characterization and theoretical studies of three apatite-type phosphates MPb4(PO4)3 (M = K, Rb, Cs)17Growth, Properties, and Theoretical Analysis of KBa2(PO3)5 Single Crystal51Deep-Ultraviolet Transparent Cs 2 LiPO 4 Exhibits an Unprecedented Second Harmonic Generation160Hydrothermal synthesis of a new lead(II) borate (Pb4O)Pb2B6O14-II5Strong Nonlinear-Optical Response in the Pyrophosphate CsLiCdP2O7 with a Short Cutoff Edge69SrNO3(OH)·H2O: A new member in strontium nitrate hydrate family with an ultraviolet cut-off edge7Cooperation of Three Chromophores Generates the Water‐Resistant Nitrate Nonlinear Optical Material Bi3TeO6OH(NO3)2113Cooperation of Three Chromophores Generates the Water‐Resistant Nitrate Nonlinear Optical Material Bi3TeO6OH(NO3)220Nonlinear Optical Rod Indium-Imidazoledicarboxylate Framework as Room-Temperature Gas Sensor for Butanol Isomers29Ba 1.31 Sr 3.69 (BO 3 ) 3 Cl: A new structure type in the M 5 (BO 3 ) 3 Cl (M = bivalent cation) system12A promising lead-free fluoride carbonate SHG material designed from a theoretical perspective16Interactions between haloperfluorobenzenes and fluoranthene in luminescent cocrystals from π-hole⋯π to σ-hole⋯π bonds54Noncentrosymmetric (NCS) solid solutions: elucidating the structure–nonlinear optical (NLO) property relationship and beyond21Tuning the inter-molecular charge transfer, second-order nonlinear optical and absorption spectra properties of a π-dimer under an external electric field21M4Mg4(P2O7)3 (M = K, Rb): Structural Engineering of Pyrophosphates for Nonlinear Optical Applications238Physicochemical Analysis of Tetrakis (Thiourea) Palladium Chloride: A Prospective Non Linear Optical Crystal8Borate-Based Ultraviolet and Deep-Ultraviolet Nonlinear Optical Crystals58Li3VO4: A Promising Mid-Infrared Nonlinear Optical Material with Large Laser Damage Threshold51Chemistry-Inspired Adaptable Framework Structures368Design and Synthesis of a Series of Novel Mixed Borate and Carbonate Halides21Two Barium Gold Iodates: Syntheses, Structures, and Properties of Polar BaAu(IO3)5 and Nonpolar HBa4Au(IO3)12 Materials5A New KBBF-Family Nonlinear Optical Material with Strong Interlayer Bonding51Finding the Next Deep-Ultraviolet Nonlinear Optical Material: NH4B4O6F1234Deep-Ultraviolet Nonlinear-Optical Material K3Sr3Li2Al4B6O20F: Addressing the Structural Instability Problem in KBe2BO3F2106Structurally stable borate as a UV nonlinear optical material20Rational Design of Deep-Ultraviolet Nonlinear Optical Materials in Fluorooxoborates: Toward Optimal Planar Configuration157Structural Design of Two Fluorine–Beryllium Borates BaMBe2(BO3)2F2 (M = Mg, Ca) Containing Flexible Two-Dimensional [Be3B3O6F3]∞ Single Layers without Structural Instability Problems14Synthesis, Structure, and Properties of Nonlinear Optical Crystal Na2SiF622[(CH3)3NH]3Bi2I9: A Polar Lead‐Free Hybrid Perovskite‐Like Material as a Potential Semiconducting Absorber54The Next‐Generation of Nonlinear Optical Materials: Rb3Ba3Li2Al4B6O20F—Synthesis, Characterization, and Crystal Growth88The Power of Heterometalation through Lithium for Helix Chain-Based Noncentrosymmetric Metal–Organic Frameworks with Tunable Second-Harmonic Generation Effects19LiGaGe2S6: A Chalcogenide with Good Infrared Nonlinear Optical Performance and Low Melting Point56Effect of Li and NH4 doping on the crystal perfection, second harmonic generation efficiency and laser damage threshold of potassium pentaborate crystals11K2[B3O3(OH)5]: A new deep-UV nonlinear optical crystal with isolated [B3O3(OH)5]2- anionic groups31Insights of BO 3 –PO 4 replacement for the design and synthesis of a new borate–phosphate with unique 1∞[Zn 4 BO 11 ] chains and two new phosphates16Noncentrosymmetric Cubic Cyanurate K6Cd3(C3N3O3)4 Containing Isolated Planar π-Conjugated (C3N3O3)3– Groups59Crystal Growth and Optical Properties of Beryllium-Free Nonlinear Optical Crystal K3Ba3Li2Al4B6O20F35A beryllium-free deep-UV nonlinear optical material CsNaMgP 2 O 7 with honeycomb-like topological layers53Ba 3 B 10 O 17 Br 2 : a new barium borate halide with B–O layered structure4BaLiZn 3 (BO 3 ) 3 : a new member of the KBe 2 BO 3 F 2 family possessing dense BO 3 triangles and the smallest interlayer distance16Cs 3 VO(O 2 ) 2 CO 3 : an exceptionally thermostable carbonatoperoxovanadate with an extremely large second-harmonic generation response130Design and synthesis of a nonlinear optical material BaAl 4 S 7 with a wide band gap inspired from SrB 4 O 764Electronic structure and large second-order non-linear optical property of COT derivatives – a theoretical exploration7First principle study of nonlinear optical crystals15K 11 RbB 28 O 48 : a new triple-layered borate with an unprecedented [B 28 O 57 ] fundamental building block19LiCs 2 La(BO 3 ) 2 and Li 3 K 9 La 3 (BO 3 ) 7 : new mixed alkali metal lanthanum borates with three-dimensional open frameworks and short cut-off edges10PbTeGeO 6 : polar rosiaite-type germanate featuring a two dimensional layered structure24Cation‐Tuned Synthesis of Fluorooxoborates: Towards Optimal Deep‐Ultraviolet Nonlinear Optical Materials191Cation‐Tuned Synthesis of Fluorooxoborates: Towards Optimal Deep‐Ultraviolet Nonlinear Optical Materials716Non-Centrosymmetric RbNaMgP 2 O 7 with Unprecedented Thermo-Induced Enhancement of Second Harmonic Generation239Visible-Light-Responsive Sillén-Structured Mixed-Cationic CdBiO2Br Nanosheets: Layer Structure Design Promoting Charge Separation and Oxygen Activation Reactions68High-Temperature, High-Pressure Hydrothermal Synthesis, Crystal Structure, Thermal Stability, and Solid State NMR Spectroscopy of an Aluminum Borate, Ba[AlB4O8(OH)]10Pushing Nonlinear Optical Oxides into the Mid-Infrared Spectral Region Beyond 10 μm: Design, Synthesis, and Characterization of La3SnGa5O14145Pb2BO3I: A Borate Iodide with the Largest Second‐Harmonic Generation (SHG) Response in the KBe2BO3F2 (KBBF) Family of Nonlinear Optical (NLO) Materials238Pb2BO3I: A Borate Iodide with the Largest Second‐Harmonic Generation (SHG) Response in the KBe2BO3F2 (KBBF) Family of Nonlinear Optical (NLO) Materials24A Series of Rare-Earth Borates K 7 MRE 2 B 15 O 30 (M = Zn, Cd, Pb; RE = Sc, Y, Gd, Lu) with Large Second Harmonic Generation Responses103M2B10O14F6 (M = Ca, Sr): Two Noncentrosymmetric Alkaline Earth Fluorooxoborates as Promising Next-Generation Deep-Ultraviolet Nonlinear Optical Materials356Recent advances in ultraviolet and deep-ultraviolet second-order nonlinear optical crystals258Deep-ultraviolet nonlinear optical materials: Development trend and innovative exploration16CsSiB3O7: A Beryllium-Free Deep-Ultraviolet Nonlinear Optical Material Discovered by the Combination of Electron Diffraction and First-Principles Calculations58The role of cations in second-order nonlinear optical materials based on π-conjugated [BO 3 ] 3− groups195Deep‐Ultraviolet Nonlinear Optical Crystal Cs2Al2(B3O6)2O: A Benign Member of the Sr2Be2(BO3)2O Family with [Al2(B3O6)2O]2− Double Layers70CaB5O7F3: A Beryllium-Free Alkaline-Earth Fluorooxoborate Exhibiting Excellent Nonlinear Optical Performances192Polar Fluorooxoborate, NaB4O6F: A Promising Material for Ionic Conduction and Nonlinear Optics495Polar Fluorooxoborate, NaB4O6F: A Promising Material for Ionic Conduction and Nonlinear Optics67Beryllium-Free Nonlinear-Optical Crystals A 3 Ba 3 Li 2 Ga 4 B 6 O 20 F (A = K and Rb): Members of the Sr 2 Be 2 (BO 3 ) 2 O Family with a Strong Covalent Connection between the ∞ 2 [Li 2 Ga 4 B 6 O 20 F] 9– Double Layers28Rb 3 VO(O 2 ) 2 CO 3 : A Four‐in‐One Carbonatoperoxovanadate Exhibiting an Extremely Strong Second‐Harmonic Generation Response208Rb3VO(O2)2CO3: A Four‐in‐One Carbonatoperoxovanadate Exhibiting an Extremely Strong Second‐Harmonic Generation Response42Assisting the Effective Design of Polar Iodates with Early Transition-Metal Oxide Fluoride Anions206Approaches to design inorganic semiconductors while maintaining structural motifs2Advantageous Units in Antimony Sulfides: Exploration and Design of Infrared Nonlinear Optical Materials95Second-order nonlinear optical crystals with mixed anions250Zn 3 P 2 S 8 : A Promising Infrared Nonlinear-Optical Material with Excellent Overall Properties70Why Some Noncentrosymmetric Borates Do Not Make Good Nonlinear Optical Materials: A Case Study with K3B5O8(OH)222Rational Design of a LiNbO3-like Nonlinear Optical Crystal, Li2ZrTeO6, with High Laser-Damage Threshold and Wide Mid-IR Transparency Window152Li2BaSc(BO3)2F and LiBa2Pb(BO3)2F with Layered Structures featuring Special Li−O/F Configurations11Na4Yb(CO3)3F: A New UV Nonlinear Optical Material with a Large Second Harmonic Generation Response8Physical Properties of a Promising Nonlinear Optical Crystal K3Ba3Li2Al4B6O20F15Two Lanthanide Borate Chlorides LnB4O6(OH)2Cl (Ln = La, Ce) with Wide Ultraviolet Transmission Windows and Large Second-Harmonic Generation Responses25Theoretical design of multifunctional half-Heusler materials based on first-principles calculations7Growth, Crystal Structures, and Characteristics of Li 5 ASrMB 12 O 24 (A = Zn, Mg; M = Al, Ga) with [MB 12 O 24 ] Frameworks12“Two in one”: an unprecedented mixed anion, Ba 2 (C 3 N 3 O 3 )(CNO), with the coexistence of isolated sp and sp 2 π-conjugated groups15A rich structural chemistry in π-conjugated hydroisocyanurates: layered structures of A 2 B(H 2 C 3 N 3 O 3 ) 4 · n H 2 O (A = K, Rb, Cs; B = Mg, Ca; n = 4, 10) with high ultraviolet transparency and strong optical anisotropy47An energy band engineering design to enlarge the band gap of KTiOPO 4 (KTP)-type sulfates via aliovalent substitution66Chloride carbodiimide K 12 Pb 51 (CN 2 ) 30 Cl 54 with an unprecedented 45 Å unit cell axis and a large birefringence7Mg(H 2 O) 6 B 4 O 5 (OH) 4 (H 2 O) 3 : a new hydrated borate with a short DUV cutoff edge9Mn-Based tin sulfide Sr 3 MnSn 2 S 8 with a wide band gap and strong nonlinear optical response30Structural insights into three phosphates with distinct polyanionic configurations20Abrupt Structural Transformation in Asymmetric ABPO4F (A = K, Rb, Cs)21Rational Design via Synergistic Combination Leads to an Outstanding Deep-Ultraviolet Birefringent Li2Na2B2O5 Material with an Unvalued B2O5 Functional Gene284BeO6 Trigonal Prism with Ultralong Be–O Bonds Observed in a Deep Ultraviolet Optical Crystal Li13BeBe6B9O2712Zeolitic Open-Framework Borates with Noncentrosymmetric Structures and Nonlinear Optical Properties24CsSbF 2 SO 4 : An Excellent Ultraviolet Nonlinear Optical Sulfate with a KTiOPO 4 (KTP)‐type Structure87CsSbF2SO4: An Excellent Ultraviolet Nonlinear Optical Sulfate with a KTiOPO4 (KTP)‐type Structure432New cadmium-selenium-oxyhalides: Noncentrosymmetric Cd5(SeO3)4Cl2(H2O) and centrosymmetric Cd2(SeO3)F2, Cd2(SeO3)(OH)Br17Module-Analysis-Assisted Design of Deep Ultraviolet Fluorooxoborates with Extremely Large Gap and High Structural Stability109Two Deep Ultraviolet Hydrated Borate Crystals: Centrosymmetric LiRbB5O8(OH)·H2O and Non-Centrosymmetric K2B5O8(OH)·2H2O8Cs3Na(H2C3N3O3)4·3H2O: A Mixed Alkali‐Metal Hydroisocyanurate Nonlinear Optical Material Containing π‐Conjugated Six‐Membered‐Ring Units68Synthesis, Structure, and Characterization of Two Mixed-Cation Quaternary Chalcogenides K2BaSnQ4 (Q = S, Se)19Rb7SrY2(B5O10)3: A Rare-Earth Pentaborate with Moderate Second-Harmonic Response and Interesting Phase-Matching Behavior29Research and Development of Zincoborates: Crystal Growth, Structural Chemistry and Physicochemical Properties20LiMII(IO3)3 (MII=Zn and Cd): Two Promising Nonlinear Optical Crystals Derived from a Tunable Structure Model of α‐LiIO399LiMII(IO3)3 (MII=Zn and Cd): Two Promising Nonlinear Optical Crystals Derived from a Tunable Structure Model of α‐LiIO337Rb10Zn4Sn4S17: A Chalcogenide with Large Laser Damage Threshold Improved from the Mn-Based Analogue28An Uncommon Hypervalent Fluorooxosilicophosphate5CsAlB 3 O 6 F: a beryllium-free deep-ultraviolet nonlinear optical material with enhanced thermal stability154Structural Origin of Thermally Induced Second Harmonic Generation Enhancement in RbNaMgP2O721Electronic and nonlinear optical features of first row transition metals-decorated all-boron B40 fullerene: A promising route to remarkable electro-optical response29A new iodate-phosphate Pb 2 (IO 3 )(PO 4 ) achieving great improvement in birefringence activated by (IO 3 ) − groups53“Old dog, new tricks”: the lone pair effect inducing divergent optical responses in lead cyanurates containing π-bonds18NaRb3B6O9(OH)3(HCO3): A Borate-Bicarbonate Nonlinear Optical Material18Syntheses, characterization, and theoretical calculation of Rb2Mg3(P2O7)2 polymorphs with deep-ultraviolet cutoff edges18Al8(BO3)4(B2O5)F8: A F-Containing Aluminum Borate Featuring Two Types of Isolated B–O Groups12Alkali-earth metal lead( ii ) oxyhalide Ba 27 Pb 8 O 8 Cl 54 exhibiting interesting [Pb 4 Ba 4 O 4 ] 8+ species8Effect of anion dimensionality on optical properties: the ∞ [B 7 O 10 (OH) 2 ] layer in CsB 7 O 10 (OH) 2 vs. the ∞ [B 7 O 12 ] framework in CsBaB 7 O 1219Control of self-organization: From equilibrium to non-equilibrium1From BaAl 2 (BO 3 ) 2 O to SnAl 2 (BO 3 ) 2 F 2 : structure transformation based on ion regulation3Helix-constructed polar rare-earth iodate fluoride as a laser nonlinear optical multifunctional material25M 4 LiBe 4 P 7 O 24 and M 4 Li(Li 3 P)P 7 O 24 (M = Cs, Rb): deep-ultraviolet nonlinear-optical phosphates with a tetrahedra-substituted paracelsian-like framework9Two new ammonium/alkali-rare earth metal difluorophosphates ALa(PO 2 F 2 ) 4 (A = NH 4 and K) with moderate birefringence and short cutoff edges26Two-stage evolution from phosphate to sulfate of new KTP-type family members as UV nonlinear optical materials through chemical cosubstitution-oriented design51KNiB4O6F3: A Layered Fluorooxoborate with Charge‐Oriented Ordering18Infrared Nonlinear Optical Polymorphs α- and β-SrCu 2 SnS 4 Exhibiting Large Second Harmonic Generation Responses with Requisite Phase-Matching Behavior44PbB5O7F3: A High-Performing Short-Wavelength Nonlinear Optical Material120Mixed-valent selenium compounds: Noncentrosymmetric Cd3(SeO3)2(SeO4) and Hg3(SeO3)2(SeO4) and centrosymmetric Pb2(SeO3) (SeO4)22Hydrogen-Bond-Assisted Reinforcement of Interlayer Connections in Zn2BO3X·H2O (X = Cl, Br): Two UV Nonlinear Optical Crystals with KBBF-Type Structure9Enhanced electronic and nonlinear optical responses of C24N24cavernous nitride fullerene by decoration with first row transition metals; A computational investigation34A review on phase transition and structure-performance relationship of second-order nonlinear optical polymorphs107Second-Order Nonlinear-Optical-Active Selenide Borate YSeBO2: Featuring a [YSeBO2]n Planar Belt39Deep-ultraviolet nonlinear optical crystals by design: A computer-aided modeling blueprint from first principles45Gadolinium-Rich Borate Gd 17.33 (BO 3 ) 4 (B 2 O 5 ) 2 O 16 Exhibiting a Magnetocaloric Effect24Nonlinear-Optical Crystal Rb3YB6O12 with Condensed B5O10 Blocks That Exhibits an Intriguing Structural Arrangement and a Short Ultraviolet Absorption Edge26First row transition metals decorated boron phosphide nanoclusters as nonlinear optical materials with high thermodynamic stability and enhanced electronic properties; A detailed quantum chemical study44Cs 3 Pb 2 (CH 3 COO) 2 X 5 (X=I, Br): Halides with Strong Second‐Harmonic Generation Response Induced by Acetate Groups75Cs3Pb2(CH3COO)2X5 (X=I, Br): Halides with Strong Second‐Harmonic Generation Response Induced by Acetate Groups22Role of Fluorooxo-Functional Units in Symmetry Breaking and Second Harmonic Generation Response Contribution in Fluorooxoborate Nonlinear Optical Crystals15Noncentrosymmetric K2Mn3(SO4)3F2·4H2O and Rb2Mn3(SO4)3F2·2H2O with pseudo-KTP structures29Highly dispersed secondary building unit-stabilized binary metal center on a hierarchical porous carbon matrix for enhanced oxygen evolution reaction23Mechanochemical Synthesis of an Ionic Cocrystal with Large Birefringence Resulting from Neutral Planar π-Conjugated Groups26Tracking and Recovery of Metal Desorption from Organized Films of Polyguanamine Derivatives having Cyclic Moieties10NaZnCO 3 (OH): A High-Performance Carbonate Ultraviolet Nonlinear Optical Crystal Derived from KBe 2 BO 3 F 2194A new nonlinear optical sulfate of layered structure: Cs2Zn2(SO4)319

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  2. Pb 2 Bi 2 GaB 3 O 11 , a new congruent-melting galloborate containing two types of asymmetric cations with a moderate birefringence

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  3. Top-Seeded Solution Crystal Growth, Morphology, Optical and Thermal Properties of Ba3(ZnB5O10)PO4

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  4. ChemInform Abstract: Designing a Beryllium‐Free Deep‐Ultraviolet Nonlinear Optical Material Without a Structural Instability Problem.

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  6. A New Deep-Ultraviolet Transparent Orthophosphate LiCs 2 PO 4 with Large Second Harmonic Generation Response

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  14. SrNO3(OH)·H2O: A new member in strontium nitrate hydrate family with an ultraviolet cut-off edge

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  15. Cooperation of Three Chromophores Generates the Water‐Resistant Nitrate Nonlinear Optical Material Bi3TeO6OH(NO3)2

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  16. Cooperation of Three Chromophores Generates the Water‐Resistant Nitrate Nonlinear Optical Material Bi3TeO6OH(NO3)2

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  17. Nonlinear Optical Rod Indium-Imidazoledicarboxylate Framework as Room-Temperature Gas Sensor for Butanol Isomers

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  18. Ba 1.31 Sr 3.69 (BO 3 ) 3 Cl: A new structure type in the M 5 (BO 3 ) 3 Cl (M = bivalent cation) system

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  19. A promising lead-free fluoride carbonate SHG material designed from a theoretical perspective

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  23. M4Mg4(P2O7)3 (M = K, Rb): Structural Engineering of Pyrophosphates for Nonlinear Optical Applications

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  32. Deep-Ultraviolet Nonlinear-Optical Material K3Sr3Li2Al4B6O20F: Addressing the Structural Instability Problem in KBe2BO3F2

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  34. Rational Design of Deep-Ultraviolet Nonlinear Optical Materials in Fluorooxoborates: Toward Optimal Planar Configuration

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  45. Crystal Growth and Optical Properties of Beryllium-Free Nonlinear Optical Crystal K3Ba3Li2Al4B6O20F

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  46. A beryllium-free deep-UV nonlinear optical material CsNaMgP 2 O 7 with honeycomb-like topological layers

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  47. Ba 3 B 10 O 17 Br 2 : a new barium borate halide with B–O layered structure

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  49. Cs 3 VO(O 2 ) 2 CO 3 : an exceptionally thermostable carbonatoperoxovanadate with an extremely large second-harmonic generation response

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