periodic table of the elements and atomic weights molecular structure of compounds theory of chemical reactions

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1 . Dw of Quu oy How ws scc of 9 cuy? Csy poc bl of ls oc wgs olcul sucu of copous oy of ccl cos glzo of wo ccs = lycl ccs yscs oycs cocp of opy opcs lcogcs bgg of cuy oy of lvy Quu oy yscs of lg: Mwll s uos Hz s ps of scg Hug pc o csy clug g swc of sg pyscs Lg s lcogc wv. oc sucu ccl bog spcoscopy

2 Isy of lg - lcboy Ro coul o b pl by Clsscl Mccs. H obc s lg = o. lcboy o lw 8π c Clsscl Rylg-s lw lvol csop pu Fucy - lc s Quu Hyposs o Dv lcboy Ro Lw. lc 9 yposz lcoc oscllo l s uz =. 8π c L of gvs Rylg-s foul. W s splc lw pcl lw:.9 lc foul ffos coffc lcboy o of 6 ppos spcu of sulg.

3 - s pl oolcoc ffc w Quu Hyposs. Hz 887 fou l sufc s lco w w lg = poolco ffc. c gy spcv of sy of lg sol of fucy s 95 pl poolcoc ffc usg lc foul. uc lg s uz poo. f f s wo fuco bl of wo fucos Mls f /.6 u 5. s 4.6 c 4.7 Cu-plocy 4.56 =.6-9

4 -4 Hyog oc pcu Cosss of vl s of Ls. os g pu s lg w spcfc fucy. l s pcl foul fo Hyog s sso spcu l Hz cos of = = 4 5 l ss -5 Rybg Foul ccous fo ll Ls Hyog oc pcu. Rybg 887: 968 c Rybg cos R H l foul c ol fo o oc spcu l c Rz s cobo ul

5 -6 Lous ogl osul M s Wvl ops yscl scpo of lg: wv-l pcl-l s oy of lvy p ogl foul p π ogl wvlg wv-pcl uly Movg pcl / p lco R α y golf bll ogl Wvs Obsv plly X y b X y ffco lco b lco b ffco M yscl scpo of lco: pcl-l.. oso obl pz w 96 wv-l.. oso obl pz w 97

6 -8 o oy of Hyog o c b s o Dv Rybg Foul o s yog o ol lc of Coulobc foc cfugl foc 4π clssclly fob ususbl oo Iouco of o-clssc coo π = = = = 4π 8π 4 8π π : ogl wvlg uzo of gul ou o us o fucy coo 977 c - R cf. R H = 968 c - R s us s oc u of gy

7 -9 Hsbg cy cpl s oso Mou of cl Co b pcf ulously w l cso Rsoluo of coscop Mou of lg p wvlg of lg plly sf o lcos p cy pcpl Coflc w o oy Cosuco of w uu oy

8 5. Hoc Oscllo Rg Roo: wo spcoscopc Mols Hoc Oscllo bol spc Foc coss of olculs Rg Roo Clsscl Rool spc o lgs oscllo uu ccl pso of gy oo 5- Hoc Oscllo Obys Hoo s Lw. f s cos f : foc cos C s C C p f s

9 5- uo fo Hoc-Oscllo Mol of Doc Molcul Cos Ruc Mss of Molcul. wo pcls coc w spg l l l co coo X X lv coo p C l f 5- Hoc Oscllo ppoo Rsuls fo pso of Iucl ol ou s Mu. l! l l l l l l l l oc s Cp ylo pso 6

10 5-4 gy lvls of Quu-Mccl Hoc Oscllo s w v = v v ω v v v zo-po gy 5-5 Hoc Oscllo ccous fo If pcu of Doc Molcul. c v v v v v v π π obs obs obs Copou / - / c - H 5 44 D H 5 Cl O C 6 O 857 4

11 5-6 Hoc-Oscllo Wv Fucos Ivolv H olyols. 4 / π! p v H v v v v v 8 4 v v vh H H H H H -5 5 v = 4 v = v = v = v H v p- / v = 5-7 H olyols v o O Fucos. vv v v * ooolz o : v : v v v v v * v v vg of poso * p v v vg of ou

12 5-8 gy Lvls of Rg Roo s. /I Rg-oo ol: bo lg ols ucg ug oo. o o π π v v I I v v gul ou c gy I L I L I L H ˆ s s s ˆ ˆ L : spcl ocs

13 5-8 gy Lvls of Rg Roo s /I. co. l l ± ± ± ± ± ± π cos π s p π 5 cos π s cos p π s p 4 π 7 5cos cos π s 5cos p 4 π s cos p 4 π 5 s p 4 π

14 5-9 Rg Roo s Mol fo Rog Doc Molcul. lco ul og oo lvls: I I I of oc olcul s g 8π I 8 π ci = ν = Hz cowv go = 6 : ool cos Mcowv bsopo spc sow sl ps vls. = = = = 4 = ν

15 . Molcul pcoscopy Mcowv bsopo spcoscopy If bsopo spcoscopy Clsscl ols ol-o lyss slco ul goup oy c. - Dff Rgos of lcogc pcu s o Ivsg Dff Molcul ocsss Rgo Mcowv F IR If s- ν / Hz λ / / c / olcul pocss oo of polyucl olcul oo of sll olcul vbo of flbl olcul lcoc so

16 - Rool sos ccopy bol sos. Hoc oscllo gy of olcul vbo Rg oo gcy gy of olcul oo c. : π / c g I / F c F

17 - Rool sos ccopy bol sos. co. lco ul w w obs obs R-bc -bc -bc R-bc vl css R R R vl ucs

18 - bo-roo Ico ccous fo ul pcg of Ls R cs of bo-roo pcu 8π R c R css w csg css < w R.68c 6.58c Fo H 7 I :

19 -4 Ls u Rool pcu o ully pc Molcul os vgoously bos lg I css cfugl soo cos Fo H 5 Cl : : D D F.44 c.4c 4 D D F F

20 -5 Ovos Obsv bol pc R R : 4 6! 4 4 R R R R R ocy cos slco ul: sy s w ov oc. obs 5.8c 99.9 c Fo H 5 Cl :

21 -6 lcoc pc Co lcoc bol Rool Ifoo gy gp bw lcoc lvls vsbl ulvol c lvl s ccop by vbol ool lvls. o-opp ppoo: lcoc ovbol lvls p. l l ol D F R R D D 4 4 obs

22 -7 Fc-Coo cpl cs Rlv Iss of boc sos = = = = = 4 Iucl sc s los ucg. F-Coo pcpl -8 Rool pcu of olyoc Molcul Dps po cpl Mos of I of Molcul Mo of ouc of I I yy I zz o of ou s I y I yz I z I y I zy I z I I I y z I I I y yy zy I I I z yz zz I I I C Dgolzo s lz fo c coo sys. pcpl o of I I I C

23 -8 Rool pcu of olyoc Molcul Dps po cpl Mos of I of Molcul. co. Rool coss: C 8π ci 8π ci spcl op sycl op sycl op I = I = I C I < I = I C pol I I I C I = I < I C fl C 8π ci C gy lvls of pol syc op F gy lvls of fl sycl op F C slco uls: olyucl olculs v sll sffss. lg cfugl soo fl spcl pol

24 -8 Rool pcu of olyoc Molcul Dps po cpl Mos of I of Molcul. co. ol sycl op

25 -8 Rool pcu of olyoc Molcul Dps po cpl Mos of I of Molcul. co. Fl sycl op

26 C of Mss Molcul Wg.84 so of I cpl Mo of I cpl s

27 -9 bos of olyoc Molculs Rps by ol Coos. slol olcul cossg g ool fo l olcul of os s of fo -6 vbol -5 fo l olcul Q F Q f 6 ol o coo Q Q Q Q Q Q H F Q Q F Q Q H ˆ ˆ 6-6 vb vb vb 6 vb vb vb

28 ol os of H O 65 c - 76 c - 6 c - lco ul: Dpol o s plll o bo s. Dpol o s ppcul o bo s.

29 uo of oo fo coupl oscllo F F f F p φ: wo-boy pol W foc popool o splc s o ccou s cll oc ppoo. :sffss M M Oscllg s ssu s soluo. ulous uos fo ll pcls. uo of : bol gy

30 Hss o ω M z y z y M z y z z z y y y z y z y z z z y y y y y M s gvco of M -. ou v o f s of golzs M -.

31 F o vo of Hss o w coo sys s sfo so vbls pss olcul ps suc s bo lg bo gl c.. M M ω M F F ω ω sfos Cs coo o l olcul coo. F s s of ps suc s scg bg c. uolly usbl. s gvco of F. ou v o f s of golzs F.

32 ul oscllo of oc olcul w w F F Hss Mo F o

33 Mss-wg Hss o M M M / / M / M / M / M - s o syc. s o oogol o c o. ω s o cssly l. W w ulply M / o bo s of uo. M s gol. M / s sly ob. M M / / M w / D Dw w D D s sycl. so-cll ycl

34 w w w w w w w w w w w w D M M F D w w M M w w ω D w w D F F ω F / / / / / / / / / / / / / ' yz F D D sfo o c o usg. Cop w Fo ul oscllo of oc olcul

35 ul oscllo of oc olcul co. ˆ W / ˆ W M X ˆ X ˆ ˆ MX X ˆ ˆ X X ss-wg coo ooolz Cs coo Cs coo olz ol ss ol sffss gul fucy * * cf.

36 ul oscllo of l oc olcul / / M M 4 ˆ X ˆ ˆ MX X ˆ ˆ X X

37 - ol Coos log o Iucbl Rpso of Molcul o oups. C v C σ v z σ v yz C z H O H σ v yz σ v z C v C σ v z σ v yz z H y z O y z H y Γ 9 - Γ = y z R R y R z vbos

38 - lco Ruls Dv fo -p ubo oy. Ψ Ψ Ψ H p ˆ -p cög uo: ubo fo lcogc fl: H cos π ˆ cos π Ψ Ψ p p wo-s Mol: y subsug o w ob Ψ Ψ H H ˆ ˆ Ψ Ψ Ψ p p p p ˆ H

39 Mulply g ov spc. ssug w ob : y = sc s sc H z z p p ˆ p * sc 4 * z z p * z z z z H so pol o ws f. - lco Ruls Dv fo -p ubo oy. co. * Ψ

40 - slco ul Rg Roo ppoo s Δ = ±. f f f cos ˆ s ˆ ; z M z M M M z o M M M - Hoc Oscllo lco Rul s Δv = ±. H H z z z ˆ / / / /

41 -4 oup oy s s o D If cvy of ol Coo bos obls I ˆ Q Q Q 6 z Q Q Q 6 QQ Q -6 ou s olly syc c s yy ps o ol o μ μ y μ z Fo w cs: sy. c b sy. c μ μ y μ z 65 c - 76 c - 6 c -

42 8. o Fuco Il ss olz fco: scbs pobbly sys s of gy. : olz cos o fuco Q: w olz sscs fs: vg gy f p Q p Q f p Q p! ] [ l

43 8- slol o Fuco of Moooc Il s s π / /. oc gy of oooc l gs: slol gy s cubc co: vg gy lc s lc s oc z y z y z y y z z y z y z y / s π 8 p 8 p 8 p p 8 s s l

44 8- Mos of os ou lcoc Roo pu. lcoc po fuco: lc p lc p olly... c.695 c 4 sco o l s of glgbl.. Ro of lu os s ss = c - vg gy f p l Q p p g lc p 4 H cpcy C R ssu l Q s uo of l gs

45 8- gy of Doc Molcul c b ppo s u of p s. lc vb o s lc vb o s! ] [ Q / s π bsl of o = bsl of vb = boo of pol bsl of lc boo of pol 8-4 Mos Molculs ou bol. Hoc oscllo ppoo: p p p p p p vb

46 8-4 Mos Molculs ou bol. co. bol pu: vb p vb vb p vb gy l vb vb vb vb p vb H Cpcy p vb vb vb C vb R p vb obbly of vbol co f C / R / = f p vb.. 4

47 8-5 Mos Molculs c Rool s. gy lvl of g oo: o fuco: o I p I gcy g Roo pu: o I o p o b pu o o / o s sll. p 8π I o g pu ppoo vg ool gy: o l o g oo g of fo s

48 8-5 Mos Molculs c Rool s. co os pobbl vlu o / f.4 = 7 fo CO s s pofl of - R- bcs of ool spcu. 8-6 Rool o Fucos Co yy ub. I suy Hooucl oc olcul Houcl oc olcul s o πm vb lc / o o o o o p vb / p / vb g l p D /

49 8-7 bol o Fuco of olyoc Molcul s ouc of Hoc Oscllo o Fucos fo c ol Coo. C vb vb vb vb vb vb vb vb vb vb vb vb p p p / p / p gfucy pu 6 5 l olcul ol olcul

50 8-8 Fo of Rool o Fuco of polyoc Molcul Dps po p of Molcul. Fo l olculs o Fo o-l olculs o 8π I π π π o o o / o o oc oc / / : syy ub spcl op I = I = I C sycl op I = I < I C sycl op I < I < I C w o I s gool pu = C. vg ol ool gy H cpcy C o o R l o R

51 8-9 Clcul Mol H Cpcs y oo g w pl D. D g M l 5 vb vb o / p / p / p π L polyoc olcul l gs 5 vb vb vb 5 vb vb vb p p p C D

52 8-9 Clcul Mol H Cpcs y oo g w pl D. co. D g M l 6 vb vb / oc o o / p / p / p π π o-l polyoc olcul l gs 6 vb vb vb 6 vb vb vb p p p C D C /R clc. C /R pl. CO CH 4..9 H O.. Mol cpcy

53 . opy co Lw of oycs - Cg of gy lo s o uffc o D Dco of poous ocss. poously pocssg ccl cos lwys oc? Dffuso of gs: Δ ΔH ly bu ogsso v pps. pls: g of gss fuso of c co of OH H 4 O c. - oulbu Isol yss volv Dco Icss Dso. poous pocss Dso of sys css. *cy fo gy o b z *cy fo so o b z fs lw lls: δ v δw C C R s s o c ffl. fo v ps o ps of go

54 - oulbu Isol yss volv Dco Icss Dso. co. C R C R cos. cos. ps o. y vg by s gvs: δv C R : opy s s fuco.

55 - l v opy s Fuco δ v v R R l δ δ v vc C vc C C δ v pocss R l C w R R l s p of p C C / R l C s pu gos low so of sys by δ v s lg.

56 -4 co Lw of oycs s opy of Isol ys Icss s Rsul of poous ocss. l gy: spoously ovs fo g- go o low- go obsv fc. + = cos. = cos. = cos. = + If > < fo > ulb s = po : pouc s sys c : gv by cg / v v v v δ δ δ δ w w δ δ δ po c po Iuly of Clusus

57 -5 Mos Fous uo of scl ocs s = l W sbl of pcs of sol syss gy gcy Ω = Ω olu ub of pcls ub of sol syss s = ub of Wys: opy: s z ulb sys. W s. ll s. lg s foul 4 Ω ol l!!!!!!! W W W W W l l! l l l l l l l sys sys sbl sbl W

58 -6 W us lwys Dvs Rvsbl ocss o Clcul opy Cgs.. F pso of gs sol pocss. fc of l pcs of ff pu... gy: opy: Hg- s ol cg opy Low- s fo v δ v v l δ δ R R R w c c l C C C C c c c c c c c 4 l l l C C C 4 c c

59 -7 oycs vs s Isg o Covso of H o Wo. g g w w δ v v v vc δ vc c vc vsbl g > c < w < c w v vc c c M ffccy ps oly o. v v -8 opy c b pss s of o Fuco. sbl l Q l Q l l Q!! l l sys

60 -8 opy c b pss s of o Fuco. co. obbly s of sys s : Moooc l gs gou s: opy p ol: p Q Q Q Q Q Q p p p p p p l l l l p p l l sys sys sbl l / l / l / π l 5! l π l π! g R R g R R g Q Q

61 -9 Molcul Foul = lw s logous o oyc Foul = δ v /. p p p Q p Q p Q Q p p p p p p p p p p v v δ δ l l l p l l l l y ffg by p fo y subsug w s gy sf og sys s ug vsbl pocss.

62 6. Ccl ulbu 6- Ccl ulbu Rsuls W bbs gy s Mu w Rspc o of Rco s ps co of co Ccl pol cos : ulbu ulbu cos Zg g g g Z Z Z Z Z Z Z Z Z Z Z Z l R

63 6- ulbu Cos s Fuco of pu Oly Z Z ulbu cos os o p o ol pssu bu cools. L Cl s pcpl covso fo -pso o c-pso: =. M c = ol L - g Cl g Cl g Cl 5 Z Z / / / / Z c c c c c c c c R c c c 6- bbs gs of Foo c b s o Clcul ulbu Coss [] [] [Z] ] [ f f f Z f H H s clcul fo s lpy of foo. s clcul fo s bsolu opy. R l

64 6-4 lo of bbs gy of Rco Mu gs of Rco s Mu ulbu g O g O O O O O O O l l R R W ol pssu s. M ppop s coos R =.479 ol - = zs ls o ulbu cos =.48 s vlu cocs w ob fo. R l O f O f 5.58 ol ol 4 l l 4 4 O f O f O O R R

65 6-5 Ro of Rco Quo o ulbu Cos Ds Dco wc Rco wll oc g g g Zg Z Z R l Z s o cssly ulbu pssu. Rco Quo: Q Q < Rco pocs fo lf o g spoously. Q > g o lf Z Z R l Q / 6-6 g of Δ o of Δ Ds Dco of Rco poy Δ < > : Rco pocs fo lf o g. Δ > < : Rco pocs fo g o lf. O4g Og Δ < : spoous ul Q = Hg Og HOg Δ < : o co wou y o.

66 6-7 o of ulbu Cos w pu s v by v' Hoff uo bbs-hlolz foul y psg bbs gy w ulbu cos H > oc g- g- H < oc g- low- Igo fo o suls: l s popool o / cf. Clusus-Clpyo uo pu-pc of H covso o pu-pc of l l R H H l l R R R R H l R H R H

67 6-8 W c Clcul ulbu Coss s of o Fucos Zg g g g Z s ps co u cos Hlolz gy: Coo fo ccl ulbu: o fuco of gs s pouc of os fo c copo. Ccl pol: W ulbu coo pso of c Z Z Z Z! Z Q Q Q Q l l l Q R R Q R Z Z Z Z

68 6-8 W c Clcul ulbu Coss s of o Fucos co.. co of oc olculs Hg Ig H HI H I HI I / 4 H o HI o I o HIg H I HI p vb / p vb / D D p HI p / R vb H D I O clculg bs o g bl o plo gs / o v H fo l slop Clc.: -.9 / ol Obs.: -.4 / ol. co of polyoc olculs o us oo pu of syc op o us vbo pus of ol os Clcul foo cos of H Og / l / l clc. l pl

69 6-9 Molcul o Fucos Rl oyc D svly bul o 6- ulbu Coss fo Rl ss pss s of l Fugcs Ccl pol of o-l gs ouco of fugcy f f R l R l f gs ps co g g ulbu coo = g H R l g f f f f Z Z H g Zg g Z f lv o s s f Z f fz R l f f f f f : oycl ulbu cos ol /M / - f /

70 6- oyc ulbu Coss pss s of cvs Ccl pol of o-l soluo ouco of cvy * R l solv of lu soluo: w * s ccl pol of pu solv Roul s s s slus of lu soluo: c w c R l s ccl pol of solu M l soluo Hy s s s l co ulbu coo = Clculo of cvy R l Z Z Z l R R Z Z Z R l : oycl ulbu cos gs ps cos ps

71 6- s of cvs Ms gfc Dffc olubly Clculos Ivolvg Ioc pcs Dssoco of uous cc c. M CHCOOH HOl HO g CHCOO c CHCOO HO CHCOO.74 H O CH COOH H O c c H CH COO CH COOH O CH COOH ppo. ± = c HO+ =. M ph =.88 Clculg ± by Dby-Hücl s lg lwi c s oc sg 5 l.7 zz I I c c / / I c c H O c CH COO c H O c CH COO c HO+ =. M s l vlu suls ± wc gvs w c HO+ vly. ± =.959 c HO+ =.7 M ph =.86 Mo ocbl o occus clculg solubly. Fo F : ppo. ± = s = M v o ± =.7 s =. M

Convergence tests for the cluster DFT calculations

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