Glossary of Terms Used in Photochemistry, 3Rd Edition (IUPAC
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Polarization Optics Polarized Light Propagation Partially Polarized Light
The physics of polarization optics Polarized light propagation Partially polarized light Polarization Optics N. Fressengeas Laboratoire Mat´eriaux Optiques, Photonique et Syst`emes Unit´ede Recherche commune `al’Universit´ede Lorraine et `aSup´elec Download this document from http://arche.univ-lorraine.fr/ N. Fressengeas Polarization Optics, version 2.0, frame 1 The physics of polarization optics Polarized light propagation Partially polarized light Further reading [Hua94, GB94] A. Gerrard and J.M. Burch. Introduction to matrix methods in optics. Dover, 1994. S. Huard. Polarisation de la lumi`ere. Masson, 1994. N. Fressengeas Polarization Optics, version 2.0, frame 2 The physics of polarization optics Polarized light propagation Partially polarized light Course Outline 1 The physics of polarization optics Polarization states Jones Calculus Stokes parameters and the Poincare Sphere 2 Polarized light propagation Jones Matrices Examples Matrix, basis & eigen polarizations Jones Matrices Composition 3 Partially polarized light Formalisms used Propagation through optical devices N. Fressengeas Polarization Optics, version 2.0, frame 3 The physics of polarization optics Polarization states Polarized light propagation Jones Calculus Partially polarized light Stokes parameters and the Poincare Sphere The vector nature of light Optical wave can be polarized, sound waves cannot The scalar monochromatic plane wave The electric field reads: A cos (ωt kz ϕ) − − A vector monochromatic plane wave Electric field is orthogonal to wave and Poynting vectors -
Donor-Acceptor Interaction and Photochemistry of Polymethylene-Linked Bichromophores in Solution
9042 J. Am. Chem. Soc. 1996, 118, 9042-9051 Donor-Acceptor Interaction and Photochemistry of Polymethylene-Linked Bichromophores in Solution Song-lei Zhang, Matthew J. Lang, Steven Goodman,† Christopher Durnell, Vlastimil Fidlar,‡ Graham R. Fleming, and Nien-chu C. Yang* Contribution from the Department of Chemistry, UniVersity of Chicago, Chicago, Illinois 60637 ReceiVed July 17, 1996X Abstract: The ground-state and the excited-state spectroscopic properties of four series of polymethylene-linked anthracene-dialkylaniline bichromophores were compared as a probe to the relationship between energetics and distance in photoinduced electron transfer (PET). The results demonstrate that, when the energy level of the charge- transfer (CT) state is lowered below that of the localized excited state by appropriate substituents, there is a strong electron-donor-acceptor (EDA) interaction in the ground state which is absent in other bichromophores. Absorption and fluorescence excitation studies revealed that there is an unusually strong EDA interaction in the ground state of A-2 which is absent in other members in the A series. When A-2 is excited directly into this EDA absorption, it exhibits two CT emissions, one at 490 nm and the other at 605 nm. The quantum yield (τf) and the lifetime (Φf) of the two emissions are dependent on the viscosity of the alkane solvent. The Φf and the τf of the 490 nm emission increased when the solvent viscosity was increased; however, those of the 605 nm emission remained essentially unchanged. The risetime of the 605 nm emission is 420 ps, but that of the 490 nm emission is instrument-function limiting. -
Lab 8: Polarization of Light
Lab 8: Polarization of Light 1 Introduction Refer to Appendix D for photos of the appara- tus Polarization is a fundamental property of light and a very important concept of physical optics. Not all sources of light are polarized; for instance, light from an ordinary light bulb is not polarized. In addition to unpolarized light, there is partially polarized light and totally polarized light. Light from a rainbow, reflected sunlight, and coherent laser light are examples of po- larized light. There are three di®erent types of po- larization states: linear, circular and elliptical. Each of these commonly encountered states is characterized Figure 1: (a)Oscillation of E vector, (b)An electromagnetic by a di®ering motion of the electric ¯eld vector with ¯eld. respect to the direction of propagation of the light wave. It is useful to be able to di®erentiate between 2 Background the di®erent types of polarization. Some common de- vices for measuring polarization are linear polarizers and retarders. Polaroid sunglasses are examples of po- Light is a transverse electromagnetic wave. Its prop- larizers. They block certain radiations such as glare agation can therefore be explained by recalling the from reflected sunlight. Polarizers are useful in ob- properties of transverse waves. Picture a transverse taining and analyzing linear polarization. Retarders wave as traced by a point that oscillates sinusoidally (also called wave plates) can alter the type of polar- in a plane, such that the direction of oscillation is ization and/or rotate its direction. They are used in perpendicular to the direction of propagation of the controlling and analyzing polarization states. -
Transition State Theory. I
MIT OpenCourseWare http://ocw.mit.edu 5.62 Physical Chemistry II Spring 2008 For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms. 5.62 Spring 2007 Lecture #33 Page 1 Transition State Theory. I. Transition State Theory = Activated Complex Theory = Absolute Rate Theory ‡ k H2 + F "! [H2F] !!" HF + H Assume equilibrium between reactants H2 + F and the transition state. [H F]‡ K‡ = 2 [H2 ][F] Treat the transition state as a molecule with structure that decays unimolecularly with rate constant k. d[HF] ‡ ‡ = k[H2F] = kK [H2 ][F] dt k has units of sec–1 (unimolecular decay). The motion along the reaction coordinate looks ‡ like an antisymmetric vibration of H2F , one-half cycle of this vibration. Therefore k can be approximated by the frequency of the antisymmetric vibration ν[sec–1] k ≈ ν ≡ frequency of antisymmetric vibration (bond formation and cleavage looks like antisymmetric vibration) d[HF] = νK‡ [H2] [F] dt ! ‡* $ d[HF] (q / N) 'E‡ /kT [ ] = ν # *H F &e [H2 ] F dt "#(q 2 N)(q / N)%& ! ‡ $ ‡ ‡* ‡ (q / N) ' q *' q *' g * ‡ K‡ = # trans &) rot ,) vib ,) 0 ,e-E kT H2 qH2 ) q*H2 , gH2 gF "# (qtrans N) %&( rot +( vib +( 0 0 + ‡ Reaction coordinate is antisymmetric vibrational mode of H2F . This vibration is fully excited (high T limit) because it leads to the cleavage of the H–H bond and the formation of the H–F bond. For a fully excited vibration hν kT The vibrational partition function for the antisymmetric mode is revised 4/24/08 3:50 PM 5.62 Spring 2007 Lecture #33 Page 2 1 kT q*asym = ' since e–hν/kT ≈ 1 – hν/kT vib 1! e!h" kT h! Note that this is an incredibly important simplification. -
Acid-Base Interactions in Wetting
J. rldlresiortSci. Tetltttol. \irl. -5.No. l. pp.57-69 ( l99l ) o VsP t9el. Acid-baseinteractions in wetting GEORGE M. WHITESIDES,*HANS A. BIEBUYCK.JOHN P.FOLKERS andKEVIN L. PRIME Departntent of Chentistry,Harvard Universiry',Cambridge, hlA 02138,USA Revisedversion received 27 Aueust1990 Abstract-The studv of the ionizationof carboxylicacid groups at the interfacebetween organic solidsand water demonstratesbroad similaritiesto the ionizationsof thesegroups in homogeneous aqueoussolution, but with importantsystematic differences. Creation of a chargedgroup from a neutralone by protonationor deprotonation(whether -NHr* from -NH, or -CO; from -CO,H) at the interfacebetu'een surface-functionalized polyethylene and \r'ateris more difficult than that in homogeneousaqueous solution. This differenceis probably related to the low effectivedielectric constantof the interface(5=9) relativeto water (e=80). It is not known to what extentthis differencein e (and in other propertiesof the interphase,considered as a thin solventphase) is reflectedin the stabilityof the organicions relativeto their neutral forms in the interphaseand in - solution,and to whatextent in differencesin the concentrationof H' and OH in the interphaseand in solution.Self-assembled monolayers (SAMs)-especially of terminallyfunctionalized alkanethiols (HS(CH:),,X) adsorbedon gold-provide model systemswith relativelywell-ordered structures thar are useful in establishingthe fundamentalsof ionizationof protic acidsand basesat the interface betr"'eenorganic solids and water.These systems,coupled r.r'ithnew analyticalmethods such as photoacousticcalorimetry (PAC) and contact angletitration, may make it possibleto disentangle some of the complex puzzlespresented by proton-transferreactions in the environmentof the organicsolid-* ater interphase. Keyx'ords:Contact ansle titration; photoacoustic calorimetrv: poly'ethylene carboxylic acid: contact angle:polvmer surfaces; u'etting; self-assembled monolavers. -
Eyring Equation
Search Buy/Sell Used Reactors Glass microreactors Hydrogenation Reactor Buy Or Sell Used Reactors Here. Save Time Microreactors made of glass and lab High performance reactor technology Safe And Money Through IPPE! systems for chemical synthesis scale-up. Worldwide supply www.IPPE.com www.mikroglas.com www.biazzi.com Reactors & Calorimeters Induction Heating Reacting Flow Simulation Steam Calculator For Process R&D Laboratories Check Out Induction Heating Software & Mechanisms for Excel steam table add-in for water Automated & Manual Solutions From A Trusted Source. Chemical, Combustion & Materials and steam properties www.helgroup.com myewoss.biz Processes www.chemgoodies.com www.reactiondesign.com Eyring Equation Peter Keusch, University of Regensburg German version "If the Lord Almighty had consulted me before embarking upon the Creation, I should have recommended something simpler." Alphonso X, the Wise of Spain (1223-1284) "Everything should be made as simple as possible, but not simpler." Albert Einstein Both the Arrhenius and the Eyring equation describe the temperature dependence of reaction rate. Strictly speaking, the Arrhenius equation can be applied only to the kinetics of gas reactions. The Eyring equation is also used in the study of solution reactions and mixed phase reactions - all places where the simple collision model is not very helpful. The Arrhenius equation is founded on the empirical observation that rates of reactions increase with temperature. The Eyring equation is a theoretical construct, based on transition state model. The bimolecular reaction is considered by 'transition state theory'. According to the transition state model, the reactants are getting over into an unsteady intermediate state on the reaction pathway. -
Polarization of EM Waves
Light in different media A short review • Reflection of light: Angle of incidence = Angle of reflection • Refraction of light: Snell’s law Refraction of light • Total internal reflection For some critical angle light beam will be reflected: 1 n2 c sin n1 For some critical angle light beam will be reflected: Optical fibers Optical elements Mirrors i = p flat concave convex 1 1 1 p i f Summary • Real image can be projected on a screen • Virtual image exists only for observer • Plane mirror is a flat reflecting surface Plane Mirror: ip • Convex mirrors make objects smaller • Concave mirrors make objects larger 1 Spherical Mirror: fr 2 Geometrical Optics • “Geometrical” optics (rough approximation): light rays (“particles”) that travel in straight lines. • “Physical” Classical optics (good approximation): electromagnetic waves which have amplitude and phase that can change. • Quantum Optics (exact): Light is BOTH a particle (photon) and a wave: wave-particle duality. Refraction For y = 0 the same for all x, t Refraction Polarization Polarization By Reflection Different polarization of light get reflected and refracted with different amplitudes (“birefringence”). At one particular angle, the parallel polarization is NOT reflected at all! o This is the “Brewster angle” B, and B + r = 90 . (Absorption) o n1 sin n2 sin(90 ) n2 cos n2 tan Polarizing Sunglasses n1 Polarized Sunglasses B Linear polarization Ey Asin(2x / t) Vertically (y axis) polarized wave having an amplitude A, a wavelength of and an angular velocity (frequency * 2) of , propagating along the x axis. Linear polarization Vertical Ey Asin(2x / t) Horizontal Ez Asin(2x / t) Linear polarization • superposition of two waves that have the same amplitude and wavelength, • are polarized in two perpendicular planes and oscillate in the same phase. -
The 'Yard Stick' to Interpret the Entropy of Activation in Chemical Kinetics
World Journal of Chemical Education, 2018, Vol. 6, No. 1, 78-81 Available online at http://pubs.sciepub.com/wjce/6/1/12 ©Science and Education Publishing DOI:10.12691/wjce-6-1-12 The ‘Yard Stick’ to Interpret the Entropy of Activation in Chemical Kinetics: A Physical-Organic Chemistry Exercise R. Sanjeev1, D. A. Padmavathi2, V. Jagannadham2,* 1Department of Chemistry, Geethanjali College of Engineering and Technology, Cheeryal-501301, Telangana, India 2Department of Chemistry, Osmania University, Hyderabad-500007, India *Corresponding author: [email protected] Abstract No physical or physical-organic chemistry laboratory goes without a single instrument. To measure conductance we use conductometer, pH meter for measuring pH, colorimeter for absorbance, viscometer for viscosity, potentiometer for emf, polarimeter for angle of rotation, and several other instruments for different physical properties. But when it comes to the turn of thermodynamic or activation parameters, we don’t have any meters. The only way to evaluate all the thermodynamic or activation parameters is the use of some empirical equations available in many physical chemistry text books. Most often it is very easy to interpret the enthalpy change and free energy change in thermodynamics and the corresponding activation parameters in chemical kinetics. When it comes to interpretation of change of entropy or change of entropy of activation, more often it frightens than enlightens a new teacher while teaching and the students while learning. The classical thermodynamic entropy change is well explained by Atkins [1] in terms of a sneeze in a busy street generates less additional disorder than the same sneeze in a quiet library (Figure 1) [2]. -
Hydride Abstraction and Deprotonation – an Efficient Route to Low Co-Ordinate Phosphorus and Arsenic Species
Hydride Abstraction and Deprotonation – an Efficient Route to Low Co-ordinate Phosphorus and Arsenic Species Laurence J. Taylor, Michael Bühl, Piotr Wawrzyniak, Brian A. Chalmers, J. Derek Woollins, Alexandra M. Z. Slawin, Amy L. Fuller and Petr Kilian* School of Chemistry, EastCHEM, University of St Andrews, St Andrews, Fife, KY16 9ST, UK E-mail: [email protected] URL: http://chemistry.st-andrews.ac.uk/staff/pk/group/ Supporting information for this article is given via a link at the end of the document. Abstract Treatment of Acenap(PiPr2)(EH2) (Acenap = acenaphthene-5,6-diyl; 1a, E = As; 1b, E = P) with Ph3C·BF4 resulted in hydride abstraction to give [Acenap(PiPr2)(EH)][BF4] (2a, E = As; 2b, E = P). These represent the first structurally characterised phosphino/arsino-phosphonium salts with secondary arsine/phosphine groups, as well as the first example of a Lewis base stabilised primary arsenium cation. Compounds 2a and 2b were deprotonated with NaH to afford low co-ordinate species Acenap(PiPr2)(E) (3a, E = As; 3b, E = P). This provides an alternative and practical synthetic pathway to the phosphanylidene-σ4-phosphorane 3b and provides mechanistic insight into the formation of arsanylidene-σ4-phosphorane 3a, indirectly supporting the hypothesis that the previously reported dehydrogenation of 1a occurs via an ionic mechanism. Introduction 4 Alkylidene-σ -phosphoranes (R2C=PR3), more commonly known as Wittig reagents, are widely used intermediates in the formation of C=C double bonds. The arsenic and phosphorus equivalents, 4 4 arsanylidene-σ -phosphoranes (RAs=PR3) and phosphanylidene-σ -phosphoranes (RP=PR3), are rare 4 by comparison. -
Transition State Analysis of the Reaction Catalyzed by the Phosphotriesterase from Sphingobium Sp
Article Cite This: Biochemistry 2019, 58, 1246−1259 pubs.acs.org/biochemistry Transition State Analysis of the Reaction Catalyzed by the Phosphotriesterase from Sphingobium sp. TCM1 † † † ‡ ‡ Andrew N. Bigley, Dao Feng Xiang, Tamari Narindoshvili, Charlie W. Burgert, Alvan C. Hengge,*, † and Frank M. Raushel*, † Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States ‡ Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322, United States *S Supporting Information ABSTRACT: Organophosphorus flame retardants are stable toxic compounds used in nearly all durable plastic products and are considered major emerging pollutants. The phospho- triesterase from Sphingobium sp. TCM1 (Sb-PTE) is one of the few enzymes known to be able to hydrolyze organo- phosphorus flame retardants such as triphenyl phosphate and tris(2-chloroethyl) phosphate. The effectiveness of Sb-PTE for the hydrolysis of these organophosphates appears to arise from its ability to hydrolyze unactivated alkyl and phenolic esters from the central phosphorus core. How Sb-PTE is able to catalyze the hydrolysis of the unactivated substituents is not known. To interrogate the catalytic hydrolysis mechanism of Sb-PTE, the pH dependence of the reaction and the effects of changing the solvent viscosity were determined. These experiments were complemented by measurement of the primary and ff ff secondary 18-oxygen isotope e ects on substrate hydrolysis and a determination of the e ects of changing the pKa of the leaving group on the magnitude of the rate constants for hydrolysis. Collectively, the results indicated that a single group must be ionized for nucleophilic attack and that a separate general acid is not involved in protonation of the leaving group. -
C-2 Ch 2 & 3 Atoms & Molecules
Molecular and Supramolecular Photochemistry Modern Molecular Photochemistry of Organic Molecules Or Principles of Photochemistry N. J. Turro, V. Ramamurthy and J. C. Scaiano Chapters 1 & 2 Photochemistry Interaction of Light with Matter (Molecules) • Organic Photochemistry • Inorganic Photochemistry • Photobiology What is the difference between thermochemistry and photochemistry? • Mode of activation • Activated by collisions (thermo) • Activated by light (photo) • Selectivity in activation • Entire molecule gets activated • Only the chromophore that absorbs the light gets activated • Energy distribution • Energy used for vibrational/rotational transition • Energy used for electronic transition only Visualization of Thermal Reactions • Transition state connects a single reactant to a single product (intermediate) and it is a saddle point along the reaction course. • Collisions are a reservoir of continuous energy (~ 0.6 kcal/mol per impact). • Collisions can add or remove energy from a system. • Concerned with a single surface. Visualization of Photochemical Reactions We need to deal with two surfaces (ground and excited state. Adiabatic Diabatic Photochemistry starts with interaction of a Photon with a Molecule • What is a photon? • What is a molecule? • How do they interact? • What are the consequences of interaction? The Basic Laws of Photochemistry Grotthuss-Draper law The First Law of Photochemistry: light must be absorbed for photochemistry to occur. Grotthus Drapper Stark-Einstein law The Second Law of Photochemistry: for each photon of light absorbed by a chemical system, only one molecule is activated for a photochemical Stark Einstein reaction. The Light Paradigm (500 BC-1850 AD) 500 2018 BC AD 55 BC 1000 1500 1700 Lucretius Newton (1643-1727) Maxwell (1831-1879) Particles! Waves! …but then came the 1900s - new people, tools, and paradigms! Paradigm 1800s: Light consists of waves (energy propagated by waves): Energy is spread over space like a liquid. -
Lecture Outline a Closer Look at Carbocation Stabilities and SN1/E1 Reaction Rates We Learned That an Important Factor in the SN
Lecture outline A closer look at carbocation stabilities and SN1/E1 reaction rates We learned that an important factor in the SN1/E1 reaction pathway is the stability of the carbocation intermediate. The more stable the carbocation, the faster the reaction. But how do we know anything about the stabilities of carbocations? After all, they are very unstable, high-energy species that can't be observed directly under ordinary reaction conditions. In protic solvents, carbocations typically survive only for picoseconds (1 ps - 10–12s). Much of what we know (or assume we know) about carbocation stabilities comes from measurements of the rates of reactions that form them, like the ionization of an alkyl halide in a polar solvent. The key to connecting reaction rates (kinetics) with the stability of high-energy intermediates (thermodynamics) is the Hammond postulate. The Hammond postulate says that if two consecutive structures on a reaction coordinate are similar in energy, they are also similar in structure. For example, in the SN1/E1 reactions, we know that the carbocation intermediate is much higher in energy than the alkyl halide reactant, so the transition state for the ionization step must lie closer in energy to the carbocation than the alkyl halide. The Hammond postulate says that the transition state should therefore resemble the carbocation in structure. So factors that stabilize the carbocation also stabilize the transition state leading to it. Here are two examples of rxn coordinate diagrams for the ionization step that are reasonable and unreasonable according to the Hammond postulate. We use the Hammond postulate frequently in making assumptions about the nature of transition states and how reaction rates should be influenced by structural features in the reactants or products.