6.  Molecular spectroscopy / Litrófsgreining sameinda; m-wave-, IR- and UV/Vis -spectra regions

6.1   Term symbols and selection rules /   Ástandstákn og valreglur

Atoms Molecules (AB) Orbital Bond axis angular momenta spin angular Total electronic angular momenta

Atoms Molecules (AB) e.g.: Orbital angular momenta Bond axis Ex amples spin angular momenta Total electronic angular momenta e.g.: Ex amples 1/2

Selection Rules

U og g u og g ástönd sameinda:

state

LW e.g: common

6.  Molecular spectroscopy / Litrófsgreining sameinda; m-wave-, IR- and UV/Vis -spectra regions

E E : : A rAB A(n=3) A(n=3) + B n = 3 n = 3 A(n=2) A(n=2) + B n = 2

A A-B E(n) n ¥ : : E(v) E(J) n=3 : n=2 E(n) : n=1 E(n)

A A-B E(n) n ¥ : E(v) E(J) n=3 n=2 E(n) n=1 E(n)

A A-B E(n) n ¥ : E(v) E(J) n=3 n=2 E(n) n=1 E(n)

A A-B E(n) n ¥ : E(v) E(J) n=3 n=2 E(n) n=1 E(n)

Energy UV/Vis region

Energy UV/Vis region

6.  Molecular spectroscopy / Litrófsgreining sameinda; 6.1 m-wave- spectra regions

rotational energy levels and transitions mwave spectrum vs. rotational energy levels and transitions J E/ energy D = 2BJ J=4 J-1 Spacing between peaks= 2BJ – 2B(J-1) = 2B D = 2B(J-1) J=3 J=2 J=0 General: J-1 -> J E(J) = BJ(J+1) Example 3 -> 4 2B Abs. mwave spectrum: 2BJ

Angular momentum Moment of Inertia

Hverfitregða Sameinda/ Moments of inertia

Angular momentum Moment of Inertia

Deviation from rigid rotar behaviour: (peaks) (Spacing between Peaks)

Polyatomic molecules

Polyatomic molecules For linear molecules

Spherical symmetric molecules Additional selection rule: DK = 0 : z Symmetric top molecules Additional selection rule: DK = 0 : Similar spectra structure

z Jy Jx Jz N H J y x J = Jx + Jy + Jz J2 = Jx2 + Jy2 +Jz2

z Iz= I|| N H y Iy= I^ x Ix= I^ Ix= Iy = I^

z H y x N E = Ex + Ey + Ez E = Jx2/2Ix + Jy2/2Iy + Jz2/2Iz E = Jx2/2I^ + Jy2/2I^ + Jz2/2I|| E = Jx2/2I^ + Jy2/2I^ + Jz2/2I^ + Jz2/2I|| - Jz2/2I^ N H y x E = J2/2I^ + Jz2/2I|| - Jz2/2I^ E = B´J2 + A´Jz2 – B´Jz2 E = B´J2 + (A´ – B´)Jz2 E = B(J(J+1)) + (A – B)K2

Spectra structure/ Útlit rófa

Simulated rotational spectrum of 12C16O at 50 K. http://www.galaxyzooforum.org/index.php?topic=279339.0

Simulated rotational spectrum of 12C16O at 1350 K. http://www.galaxyzooforum.org/index.php?topic=279339.0

Perchloryl Fluoride, FClO3 http://www.astro.uni-koeln.de/site/vorhersagen/pickett/beispiele/FClO3/

Örbylgjulitrófsgreining Fjölatóma sameinda: Kúlu-og top-samhv. Örbylgjulitrófsgreining Fjölatóma sameinda:

http://www. aanda. org/articles/aa/full/2006/43/aa5777-06/aa5777-06 http://www.aanda.org/articles/aa/full/2006/43/aa5777-06/aa5777-06.fig.html

Information derived from mwave spectra:

Örbylgjulitróf efnanna AB = CH, OH, CO og NO, í geimryki: EEB Örbylgjulitróf efnanna AB = CH, OH, CO og NO, í geimryki: Tegunda- og hitagreiningar Ákvarða AB, T Litrófsstuðlar efna eru: Efni / sameindir B 1) D 1) CH 14.46 0.00145 OH 18.91 19.4E-4 CO 1.931 0.00000636 NO 1.672 0.54E-6 1) http://webbook.nist.gov/chemistry/form-ser.html.en-us.en

Örbylgjulitróf efnanna AB = CH, OH, CO og NO, í geimryki: EE4 Örbylgjulitróf efnanna AB = CH, OH, CO og NO, í geimryki: Tegunda- og hitagreiningar Ákvarða AB, T Litrófsstuðlar efna eru: Efni / sameindir B 1) D 1) CH 14.46 0.00145 OH 18.91 19.4E-4 CO 1.931 0.00000636 NO 1.672 0.54E-6 1) http://webbook.nist.gov/chemistry/form-ser.html.en-us.en

OH

OH

OH 150

6.  Molecular spectroscopy / Litrófsgreining sameinda; 6.3 IR- spectra regions

Útlit rófa vs Upplausn / Spectra structures vs. resolution: Útl.rófa(1) Útlit rófa vs Upplausn / Spectra structures vs. resolution:

Skammtaþrep efnatengja / quantum levels: Titr.þrep Skammtaþrep efnatengja / quantum levels: Snúnings-og titringsþrep/ rotational and vibrational levels: Titringsþrep / vibrational levels:

Útlit IR rófa / IR spectral structure Útl.rófa(2) Tilurð IR rófa / Energy transitions: Útlit IR rófa / IR spectral structure

HCl: H35Cl/H37Cl; IR róf/spectra (H.Í.):

HCl(2)

IR róf línulegra sameindir / IR spectra for linear molecules: H-C=C-H: H-C=N:

IR róf topsamhverfra sameinda / IR spectra for symmetric top molecules: CH3I:

6.  Molecular spectroscopy / Litrófsgreining sameinda; 6.4 UV/Vis -spectra regions

A A-B E(n) n ¥ : : E(v) E(J) n=3 : n=2 E(n) : n=1 E(n)

What is hidden in the flame? Flame / Introduction a. Molecular brake down b. Thermodynamics c. Emission II. Emission spectrum a. Cause of emission b. Emitters(?) c. Information derived from spectra analysis(?)

(e: the flame) / increasing O2

/i.e.: soot https://www.linkedin.com/pulse/black-soot-port-harcourt-rivers-state-nigeria-tamuno-esq-s-j-d-?articleId=8734102024765501037

C60 C70 http://blog.zacharyabel.com/tag/fullerenes/ http://depositphotos.com/12083166/stock-photo-fullerene-c70-molecular-structure.html

/ exothermic reactions: / energy / energy / products / reaction path

/energy released /as /kinetic energy /increasing temperature /light energy /how?

/NB: /products /reactive radicals are formed /molecular fragments

=> Increasing temperature / excess kinetic energy: / excess vibrational energy / excess rotational energy / excess translational energy

/- potential energy = electron energy loss /energy transfer /emission

/energy transfer: /emission following electron transfer: /electron to kinetic energy transfer: / II. The flame spectrum Flame rich in oxygen => blue coloured:

/inlet slit /PMT /comp. /Mono- chromator / gas burner

Continuous radiation Samfellt ljós Na H Hg Cu Lífrænt efni/ organic compound

/ “outer flame” / “inner flame” / spectrum / “inner flame”

/ “outer flame” / “inner flame” / “outer flame”

/ “inner flame”

/ more detail: / i.e.:

Chemiluminescence / Hvarfljómun Energy Path or / Chemiluminescence Analogy: Fluorescence

Chemiluminescenec / Hvarfljómun Energy Path or / Chemiluminescence Example / Flame:

Chemiluminescenec / Hvarfljómun Energy Path or / Chemiluminescence Example / Excimer laser processes:

photochemistry example: Ljósefnafræði ; Dæmi / photochemistry example: Cl H Xe

photochemistry example: Ljósefnafræði ; Dæmi / photochemistry example: . Cl H . Xe .

photochemistry example: Ljósefnafræði ; Dæmi / photochemistry example: Xe Cl H

photochemistry example: Ljósefnafræði ; Dæmi / photochemistry example: + - Cl Xe H

photochemistry example: Ljósefnafræði ; Dæmi / photochemistry example: Xe Cl H

CO2 and Excimer LASERs

Chemiluminescenec / Hvarfljómun Energy Path or / Chemiluminescence Example / Lucifer: Lucifer Luciferase E

http://emmybella.wordpress.com/production-of-light/

Firefly Luciferase Catalyzed Rxn Yellow-green light λmax = 560 nm (Figure 2) Citation 2

ATP + H2O – ADP + Pi ATP: Pi Many resonance figures; ATP/ADP ATP + H2O – ADP + Pi Repulsion forces; instability High energy state Pi Many resonance figures; stability; low energy state

2 H2O2 → O2 + 2 H2O Fe+ http://en.wikipedia.org/wiki/Luminol

http://en.wikipedia.org/wiki/Luminol http://science.howstuffworks.com/luminol1.htm

Pre- dissoc- iation Predissociation ? Emission spectrum Distorted:

Ljósrof:

Links to spectra simulation programs: PGOPHER IGOR m-wave m-róf 1.03; IGOR file IR PGOPHER  "HCl/DCl 1.04; IGOR file" UV/VIS (rot. Structure) UV-róf 2 /ROT 1 UV/VIS; FCF (vibr. Structure) Bound -> Bound 2.1 /FCF 1