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  • Molekula

    An electrically neutral en0ty consis0ng of more than one atom (n > 1). Rigorously, a molecule, in which n > 1 must correspond to a depression on the poten0al energy surface that is deep enough to confine at least one vibra0onal state. (IUPAC Gold Book)

  • Molekula H2 kivka potenciln energie E = f(R)

    vznik molekula (minimum)

    vazebn vzdlenost

    vazebn energie

    nevznik molekula

    dEdr

    = 0

    Kovalentn vazba vznik v dsledku innho pekryvu elektronovch obal atom

    1

    1*

    vazebn molekulov orbital

    protivazebn molekulov orbital

    Ene

    rgie

    1s 1s

    Vazebn d (Bond Order)

    BO =nbonding nantibonding

    2

    Atkins 10

  • Molekula H2 kivka potenciln energie E = f(R)

    vznik molekula (minimum)

    vazebn vzdlenost

    vazebn energie

    nevznik molekula

    dEdr

    = 0 hYp://www.forgoYenplanet.com/studyguide/chem210/chem210_ch3.html

    Energe1ck pspvky (mol. Ion H2+)

  • MO orbital

    je vlcov symetrick podle spojnice atomovch jader a m zvenou el. hustotu na spojnici jader

    Atkins 10.3.2.1

  • - orbitaly

    v rovin spojnice jader je nulov el. hustota nad a pod n je zven el. hustota monost snadn degenerace

    Atkins 10.3.2.2

  • Nsobn vazby

    mezi dvma partnery me vzniknout i vce vazeb hovome o nsobnch vazbch jednoduch vazba (obvykle ) dvojn (obvykle a ) trojn (obvykle a 2)

    CH3 CH3

    CH2 CH2

    CH CH

    d E

  • Charakteristiky vazeb

    dlka 10 -10 m energie kJ.mol -1 dlka 10 -10 m energie kJ.mol -1

    C-H 1.10 373 N-H 1.01 390 C-C 1.54 348 N-N 1.48 159 C=C 1.34 620 N=N 1.26 419 C C 1.20 814 P-H 1.40 319 C-F 1.40 473 O-H 0.96 466 C-Cl 1.76 331 S-H 1.30 348 C-Br 1.94 277 Si-H 1.50 318 C-I 2.13 239 Si-F 1.80 542 C-N 1.47 293 Si-Cl 2.10 361 C=N 1.27 616 Si-Br 2.30 289 C-O 1.43 344 Si-I 2.50 214 C=O 1.21 708 C-Hg 2.10 218

    dlka bn kovalentn vazby: 100-200 pm, bn energie kovalentn vazby ~400 kJ/mol

  • Homonuklern dvouatomov mol. Atkins 10.3.2.4

  • Heteronuklern molekuly

    1s

    *

    2px 2py 2pz

    n

    H

    F +

    +

    _

    S = 0, nulov pekryvov

    integrl

    kombinuj se orbitaly s podobnou energi

  • Elektronick stavy molekul

    Elektrony obsazuj molekulov orbitaly (, *, , *, n)

    Lze je mit fotoelektronovou spektroskopi

    Atkins 10.3.2.5

  • XPS

    m prvkov sloen, empirick vzorec, chemick a elektronick stav prvk v materilu (men vyaduje velmi vysok vakuum UHV)

  • UV/VIS spektra molekul Excitace elektron UV/VIS fotony

    Wozniak B., Dera J. (2007). Atmospheric and Oceanographic Sciences Library. New York: Springer Science+Business Media. LLC. ISBN 978-0-387-30753-4.

    Atkins 13

  • UV/VIS Spektroskopie I0 I

    T =II0,

    transmitance

    dI = cIdldII

    = cdl, dIII0

    I = c 0

    L dl

    ln II0,

    = cL, logII0,

    = cL, ln(10) =

    logT = A = cLA absorbance Lambertv-Beerv zkon

    Atkins 13.1.1

    L

    molrn absorpn koeficient c koncentrace L dlka opt. drhy

  • UV/VIS Spektrum

    -0.1

    0

    0.1

    0.2

    0.3

    0.4

    0.5

    0.6

    0.7

    250 350 450 550 650 750

    vlnov dlka (nm)

    abso

    rban

    ce

    koncen

    trace

    Atkins 13.1.1

    mn citliv na zmnu koncentrace

    velmi citliv na zmnu koncentrace

    591 nm 303 nm

  • Lambertv-Beerv zkon

    y = 65523xR2 = 0.9976

    y = 15928xR2 = 0.9966

    0.0

    0.1

    0.2

    0.3

    0.4

    0.5

    0.6

    0.7

    0.0E+00 2.0E-06 4.0E-06 6.0E-06 8.0E-06 1.0E-05 1.2E-05

    Koncentrace (mol/l)

    abso

    rban

    ce

    (591nm)

    65523

    dm3.mol-1.cm-1

    (303nm)

    15928

    dm3.mol-1.cm-1

    vypoteno

    linern regres

    krystalov viole

    Atkins 13.1.1

    pro 591nm

    pro 303 nm

    A = cL

  • UV/VIS spektra molekul Spektra jsou spojit ne arov jako u atom

    Wozniak B., Dera J. (2007). Atmospheric and Oceanographic Sciences Library. New York: Springer Science+Business Media. LLC. ISBN 978-0-387-30753-4.

    Atkins 13

  • Vnitn pohyb molekul

    hYp://2012books.lardbucket.org/books/principles-of-general-chemistry-v1.0m/s22-04-entropy-changes-and-the-third-.html

  • Ukzka vibrac molekuly vody

  • Molekuly maj vibran a rotan stavy Stupn volnos0 3N (poet atom/jader)

    3 translan (v osch x, y, z) 3 rotan (pro linern 2 rotan) 3N-6 (3N-5 pro linern) vibranch stup

    Vibran o rotan stavy jsou kvantovan

    En = n+12

    !

    "#

    $

    %&hc , n = 0, 1... EJ = J J +1( )hcB, J = 0, 1...

    vibran kvantov slo

    vibran frekvence

    rotan kvantov slo

    rotan konstanta

    E0 =12hc

    En+1 En = hc

    Energie zkladn vibran hladiny

    hladiny jsou ekvidistantn

    Harmonick osciltor Rigidn rotor

    Atkins 8.2, 8.3

    Energie zkladn rotan hladiny = 0

  • Rotan-vibran struktura

    E0 =12hc

    Vy vibran hladiny nejsou ekvidistantn - anharmonicita

    disocian energie vazby

    Atkins 12

  • McQuarrie, Simon: Physical Chemistry, A Molecular Approach

    Rotan konstanta Vibran vlnoty vzdlenost energie

  • Osud elektronick excitan energie

    Jablonskiho diagram (monomolekulrn relaxan procesy)

    Emisn spektra vykazuj erven posun Fluorescence krat dosvit ne fosforescence (spinov zakzan pechod)

    Pi excitaci se nemn spin a geometrie (Franck-Condonv princip, ver0kln pechod)

    Atkins 13.2

  • rotace vibrace elektronov pechody NMR XPS

  • Polarizovan svtlo Atkins 13.1.3.4

  • Polarimetrie Op0cky ak0vn ltky st rovinu polarizovanho svtla - vyui} nap. sacharimetrie

    [ ]T=100lcm

    lcm

    specifick otivost, pi dan telot a vlnov dlce

    hel otoen

    dlka op0ck drhy

    hmotnostn koncentrace, nap. v g/L

  • Cirkulrn dichroismus (CD) M rozdl v absorpci levo- a pravo-toivho cirkulrn polarizovanho svtla

    Nat. Protoc. 2006; 1(6): 28762890.

    Circular dichroism (CD) spectra of polypep0des and proteins with representa0ve secondary structures. a, CD spectra of poly-L-lysine at pH 11.1 in the 1 (black) -helical and 2 (red) an0parallel -sheet conforma0ons and at pH 5.7 in the 3 (green) extended conforma0ons5 and placental collagen in its 4 (blue) na0ve triple-helical and 5 (cyan) denatured forms64. b, CD spectra of representa0ve proteins with varying conforma0ons: 1 (black) sperm whale myoglobin; 2 (green) chicken heart lactate dehydrogenase; 3 (red) bovine -chymotrypsin and 4 (cyan) human Bence Jones protein REI light chain, which is a human immunoglobulin light chain of type. Spectra are from data sets supplied by Dr. W.C. Johnson.

  • Cirkulrn dichroismus (CD) Sklad protein (protein fold) denaturace/renaturace

    hYp://strubi.uni-graz.at/projects/all.htm

  • Plocha potenciln energie (PES) Atkins 22.3.2

  • Chemie turistika po hyperplochch

    katalza kine0cky/termodynamicky

    zen dj

    Plocha potenciln energie (PES) energe0cky minimln reakn cesta

    Atkins 22.3.2

    TERMODYNAMIKA

    KINETIKA

  • Reakn koordinta

    A geometric parameter that changes during the conversion of one (or more) reactant molecular en00es into one (or more) product molecular en00es and whose value can be taken for a measure of the progress of an elementary reac0on (for example, a bond length or bond angle or a combina0on of bond lengths and/or bond angles; it is some0mes approximated by a non-geometric parameter, such as the bond order of some specified bond). (IUPAC Gold Book)

    Atkins obr. 21.13

  • Ukzka SN2 reakce

    Ukzka SN1 reakce

  • Dynamika vibrac/disociace NaI

    Femtosecond spectroscopic results for the reac0on in which NaI separates into Na and I. The full circles (lower set of data) are the absorp0on of the complex and the open circles the absorp0on of the Free atoms (A.H. Zewail, Science, 242 (1988) p.1645).

  • Individuln reakce

    ne kad reakce je produk0vn

    pi excitaci pechzme na jin PES jin tvar jin chemie fotochemie

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