NearSymmetry in our Universe The origin of life

Near-Symmetry in our Universe: The origin of life and the preponderance of matter over antimatter P. R. Bunker Columbus 2008 Wednesday 18 June

One nucleus and one electron in a molecule Molecular Centre of Mass +Ze Fem -e Fem is the electromagnetic force between them

Parity (or Inversion) Symmetry -e +Ze C of Mass Fem’ Fem -e +Ze Fem’ = Fem so PHem = Hem. P and parity (+/-) is a symmetry label.

+ Parity - Parity Ψ+(x) Ψ-(x) x x Ψ-(-x) = -Ψ-(x) Ψ+(x) x + + Ψ (-x) = Ψ (x) Symmetry of eigenfunctions restricted by symmetry of Hamiltonian

A simple result of the Parity Symmetry of the Ψ Cs 7 s(+) ------- Electric dipole transition moment = 0 6 s(+) ------- This is completely forbidden as an electric dipole transition since the electric dipole moment μ has (-) parity. ∫Ψ+(7 s)μΨ+(6 s)dτ = 0

HOWEVER If we include the effect of the weak neutral current interaction -e +Ze C of Mass Few’ Few -e +Ze Few’ ≠ Few PHew – Hew. P = δ and parity (+/-) is not a perfect symmetry label

Parity Near-Symmetry or Parity-Violation Helectroweak mixes small amount of (-) parity states into each (+) state. Cs 7 s ------- F = 4 Electric dipole transition moment = 2. 05(5) x 10 -11 D 6 s ------- F = 3 Wood et al. , Science 275, 1759 (1997) and Can J Phys 77, 7 (1999). Linz et al. , Eur Phys J A 32, 525 (2007) An ab initio ‘Standard Model’ calculation gives better than 1% agreement with experiment. See Dzuba et al. , Phys Rev A 73, 022112 (2006)

The effect of P-violation for a chiral molecule: CHFCl. Br F F Cl Cl Br Enantiomers R Br S CF stretching frequency ν 4 ~ 32 THz Theory says ν 4(R) ≠ ν 4(S) because of parity-violation.

P-violation in chiral molecules Suggested in 1975 by V. Letokhov: Phys. Lett. 53 A, 275 (1975); O. N. Kompanets et al, Opt. Commun. 19, 414 (1976); First experiment on camphor: Arimondo et al Opt. Commun. 23, 369 (1977), precision 10 -8 Latest experiments CHFCl. Br: Ch. Daussy et al. , Phys. Rev. Lett. 83, 1554 (1999); M. Ziskind et al, . Eur. J. Phys. D 20, 219 (2002): Strong n 4 CF stretching mode which matches the R(14)-branch of the 9. 4 mm CO 2 laser band (1071 cm-1). Resolution is a few Hz, and precision is about 10 -13. Experiments by Ch. Chardonnet and co-workers on CHFCl. Br

P-violation in chiral molecules Suggested in 1975 by V. Letokhov: Phys. Lett. 53 A, 275 (1975); O. N. Kompanets et al, Opt. Commun. 19, 414 (1976); First experiment on camphor: Arimondo et al Opt. Commun. 23, 369 (1977), precision 10 -8 Latest experiments CHFCl. Br: Ch. Daussy et al. , Phys. Rev. Lett. 83, 1554 (1999); M. Ziskind et al, . Eur. J. Phys. D 20, 219 (2002): Strong n 4 CF stretching mode which matches the R(14)-branch of the 9. 4 mm CO 2 laser band (1071 cm-1). Resolution is a few Hz, and precision is about 10 -13. Experiments by Ch. Chardonnet and co-workers on CHFCl. Br

Calculation of Δν 4 for CHFCl. Br Calculated frequency difference: Δν 4 = ν 4(R) – ν 4(S) = 2. 4 m. Hz Precision required: Δν 4 / ν 4 ~ 10 -16 Trap molecule and use optical frequency comb

Deceleration of a large molecule in a high-field seeking state Talks TF 10 and TG 04 Wohlfart, Grätz, Filsinger, Haak, Meijer, Küpper, Phys. Rev. A 77, 031404(R) (2008)

New ab initio calculations by D. Figgen and P. Schwertdfeger Barrier (cm-1) SOHF Dip. Mom (D) ΔEPV(S) (Hz) Mol. Wt. (u) 23000 2. 5 -0. 012 68 Se. OHF 19000 3. 3 -0. 10 116 Se. OCl. I 8500 2. 3 7. 8 258 Need 1 D for every 20 u

New ab initio calculations by D. Figgen and P. Schwertdfeger Barrier (cm-1) SOHF Dip. Mom (D) ΔEPV(S) (Hz) Mol. Wt. (u) 23000 2. 5 -0. 012 68 Se. OHF 19000 3. 3 -0. 10 116 Se. OCl. I 8500 2. 3 7. 8 258 Need 1 D for every 20 u

New ab initio calculations by D. Figgen and P. Schwertdfeger Barrier (cm-1) SOHF Dip. Mom (D) ΔEPV(S) (Hz) Mol. Wt. (u) 23000 2. 5 -0. 012 68 Se. OHF 19000 3. 3 -0. 10 116 Se. OCl. I 8500 2. 3 7. 8 258 Need 1 D for every 20 u

Amino acid molecules are chiral R R L D R = CH 3, CH 2 OH, CH 2 SH, CH(CH 3)2, …

Protein molecules NH Protein molecules consist of up to about 10000 amino acid molecules joined together by peptide bonds. CO R The amino acid molecules in proteins are all L Peptide bond Also the sugar molecules In DNA are all D There is “Homochirality” As a result all protein and DNA molecules are HELICAL R’ NH CO

HOMOCHIRALITY IS A BIG PROBLEM How did Mother Nature arrange chemical evolution on the earth to give only L-amino acids and D-sugars?

Biomols of Life are Homochiral (D-sugars and L-amino acids) A Connection? Parity Violating Weak Neutral Current Interaction causes E(D) ≠ E(L)

The Yamagata Hypothesis (1966) E(D-sugars) < E(L-sugars), and E(L-amino acids) < E(D-amino acids). Leads to the required homochirality Calculations reveal no clear evidence for this. And it ain’t so simple See Wesendrup, Laerdahl, Compton and Schwerdtfeger, J. Phys. Chem. A 2003, 107, 6668.

No Connection (on Earth) with P-violation if Life Came from Outer-Space! Svente Arrhenius, Die Umschau 7, 481 (1903). “PANSPERMIA” Palmer, Nature (1996) 383, 221.

Life develops in < 0. 5 Gyr? Meteor impacts First Eukaryotes (cells contain a nucleus) First Prokaryote (bacteria) 1 0. 1 PO (atm) 2 First unambiguous evidence for life 0. 01 Fossil microorganisms In Ontario, Canada. Tyler and Barghoorn, Science 119, 606 (1954) 0. 001 rise of O 2 0. 0001 Nature 448, 1005(2007) 0. 00001 4. 5 4 3. 5 Earth begins (- 4. 56 Gyr) 3 2. 5 2 1. 5 1 Time before Present / 109 years 0. 5 0

Reduced 13 C in rocks that formed more than 3. 7 Gyr ago in Isua Greenland is possibly the oldest evidence of life on earth. Much controversy. See Science 308, 366 (2005), Nature 434, 155 (2005). Age of the earth: 4. 56 Gyr: Allègre Phil Trans RSL. A 359, 2137 (2001) Wilde et al. Nature 409, 175 (2001) Forming planets: Nature 448, 1003 and 1022 (2007) Impacts on early earth: Nature 342, 139 (1989) Science 312, 1133 (2006) 300 ton/yr organic stuff 5000 ton/yr 4. 5 Gyr ago

Development of an Enantiomeric Excess ENERGETIC PREFERENCE • ΔE from parity violation, (Yamagata 1966). BIOLOGICAL EVOLUTION • `Killer enzymes’ ENVIRONMENTAL EFFECT • • Circularly polarized radiation, (Le Bel 1874, Van’t Hoff, Vester, Deutsch, Bonner). Formation on an asymmetric surface, (Palache, Flores, Wächtershäuser, Hazen, Zepik). STATISTICAL FLUCTUATION

Amplification of an Enantiomeric Excess • Crystallization, (Landolt 1896, Viedma 2005) • Autocatalytic reaction, (Strong 1898, Frank, Soai, Saghatelian 2001)

Excess of one form Amplified by an Autocatalytic Reaction A + B L catalyzed by L inhibited by D A + B D catalyzed by D inhibited by L • Strong in Nature 59, 53 (1898). • Frank in Biochem. Biophys. Acta. 11, 459 (1953). • Soai et al. in Nature 378, 767 (1995) and in The Chemical Record 1, 321 (2001), 2% excess of L-pyrimidyl alcohol amplified to 89%.

Excess of one form Amplified by an Autocatalytic Reaction A + B L catalyzed by L inhibited by D A + B D catalyzed by D inhibited by L • Strong in Nature 59, 53 (1898). • Frank in Biochem. Biophys. Acta. 11, 459 (1953). • Soai et al. in Nature 378, 767 (1995) and in The Chemical Record 1, 321 (2001), 2% excess of L-pyrimidyl alcohol amplified to 89%. LAST UNIVERSAL COMMON ANCESTOR (LUCA)

Development of an Enantiomeric Excess ENERGETIC PREFERENCE • ΔE from parity violation, (Yamagata 1966). BIOLOGICAL EVOLUTION • Killer enzymes ENVIRONMENTAL EFFECT • • Circularly polarized radiation, (Le Bel 1874, Van’t Hoff, Vester, Deutsch, Bonner). Formation on an asymmetric surface, (Palache, Flores, Wächtershäuser, Hazen, Zepik). STATISTICAL FLUCTUATION

Stereoselective Photochemical Reactions Caused by Circularly Polarized Radiation CPR observed to have a weak stereoselective effect in the lab. . J. Phys. B 40, 3425(2007), PRA 69, 062717(2004), SPIE conf 2007 Bonner, Mayo Greenberg and Rubenstein in Origins of Life and Evol. of Biospheres 29, 215 (1999): CP synchrotron radiation from electrons orbiting a neutron star shining on organic mantles of interstellar grains causes e. e. All 19 L-amino acids absorb preferentially left-handed CPR in the UV. This extraterrestrial e. e. is then delivered to earth by interplanetary dust particles, comets or meteors.

Bailey et al. , Science 281 (1998) 672 arc sec Total Infrared intensity Percentage circular polarization A star-forming region in the Orion nebula The Becklin Neugebauer object

Bailey et al. , Science 281 (1998) 672 arc sec Total Infrared intensity Percentage circular polarization A star-forming region in the Orion nebula Astronomical UV UVmeasurements observations with Astronomical withpolarimeter needed!

Bailey et al. , Science 281, 672(1998) The Murchison meteorite has an e. e. of L-amino acids: Science 275, 951 (1997), Nature 394, 236 (1998)

Let‘s consider some other symmetries that are, or might be, only near-symmetries Implications in high res mol spec

Inversion P -e +Ze C of Mass F’ Force=F -e P +Ze Standard Model gives (F’ – F) to within 1% Parity violation is understood

Then charge conjugation C +e +Ze C of Mass F” F -e CP -Ze In the Standard Model (F” – F) is very small

Then time reversal T +e +Ze C of Mass F F -e TCP -Ze In Standard Model TCP is true symmetry

TCP symmetry Positron Proton +e +e Anti proton Electron -e -e H atom anti H atom ν(1 S-2 S) in H = ν(1 S-2 S) in anti-H See Gabrielse et al, PRL 100, 113001 (2008) “Anti-H Production within a Penning-Ioffe Trap”

CP-Violation CP-violation would account for the fact that the universe does not consist of equal amounts of matter and antimatter. (Sakharov, Sov. Phys. JETP Letters, 5, 24 1967). However, the Standard Model does not have enough CP-violation See, for example, Trodden, Rev Mod Phys 71, 1463 (1999)

Measurement of CP-Violation Can measure CP-violation using High Resolution Molecular Spectroscopy Because of TCP symmetry lets talk in terms of T-violation

Hudson, Sauer, Tarbutt and Hinds, PRL 89 (2002) 023003 + 174 Yb. F - Energies of m. F = ± 1 split by T-violation I(174 Yb)=0, I(F)=1/2, ground state is 2Σ v=0, N=0 level has hfs with F = 0 and 1. In an E-field F =1 has m. F = 0 and ± 1 components. Splitting Δ = 2 de Eeff Electric dipole moment of an electron Effective electric field at electron is huge in a heavy polar diatomic molecule

Quantum Chemical Calculation of Eeff for Yb. F Mosyagin, Koslov and Titov, J. Phys. B. 31 (1998) L 763 In external field > 20 k. V/cm they calculate Eeff = 25 GV/cm So splitting of m. F = ± 1 levels is: Δ = 2 Eeff de Standard Model value of de = 2 x (25 GV/cm) x (~10 -30 D) ~ 50 × 10 -15 Hz

Quantum Chemical Calculation of Eeff for Yb. F Mosyagin, Koslov and Titov, J. Phys. B. 31 (1998) L 763 In external field > 20 k. V/cm they calculate Eeff = 25 GV/cm So splitting of m. F = ± 1 levels is: Δ = 2 Eeff de Standard Model value of de = 2 x (25 GV/cm) x (~10 -30 D) ~ 50 × 10 -15 Hz (5 x 10 -19 D) Minimal Supersymmetric Standard Model value of de

Quantum Chemical Calculation of Eeff for Yb. F Mosyagin, Koslov and Titov, J. Phys. B. 31 (1998) L 763 In external field > 20 k. V/cm they calculate Eeff = 25 GV/cm So splitting of m. F = ± 1 levels is: Δ = 2 Eeff de = 2 x (25 GV/cm) x (5 × 10 -19 D) ~ 24 m. Hz MSSM value of de Exp. limit |de| ≤ 10 -17 D in PRL 89, 023003 (2002). Stark decelerator used: PRL 92, 173002 (2004) See Hudson et al http: //arxiv. org/pdf/physics/0509169 (An experiment on atomic Thallium gives |de| ≤ 10 -18 D)

Quantum Chemical Calculation of Eeff for Yb. F Mosyagin, Koslov and Titov, J. Phys. B. 31 (1998) L 763 In external field > 20 k. V/cm they calculate Eeff = 25 GV/cm So splitting of m. F = ± 1 levels is: Δ = 2 Eeff de = 2 x (25 GV/cm) x (5 × 10 -19 D) ~ 24 m. Hz MSSM value of de Exp. limit |de| ≤ 10 -17 D in PRL 89, 023003 (2002). Stark decelerator used: PRL 92, 173002 (2004) See Hudson et al http: //arxiv. org/pdf/physics/0509169 (An experiment on atomic Thallium gives |de| ≤ 10 -18 D)

Other CP-violation tests Excited electronic state of Pb. O Electric dipole moment of the neutron Tevatron in Batavia Illinois Large Hadron Collider at CERN

The Symmetrization Postulate Fermions: Only antisymmetric states Bosons: Only symmetric states Pauli Exclusion Principle, nuclear spin stat. weights and missing levels. Can it breakdown? Fermi’s idea. They are not completely identical Another idea involves para-statistics and quons: See Greenberg and Delgardo, Phys Lett A 288, 139 (2001) One of the Failures of the Standard Model.

Exchange-symmetric states of He Gordon Drake, Phys. Rev. A 39 (1989) 897. Exchange symmetric states are called “paronic” states. They violate the Pauli Exclusion Principle. Gordon has calculated their energies.

Exchange-symmetric states of He

Exchange-symmetric states of He Atomic beam fluorescence experiment does not see transition from paronic state. Violation of PEP < 5 10– 5. PRL 74, 4787 (1995)

Exchange-antisymmetric states of CO 2 For the CO 2 molecule states with odd values of J are missing because 16 O nuclei are Bosons. Mazzotti et al. PRL 86, 1919 (2001) looked for one: (0001)-(0000) R(25) calc at 2367. 265 cm-1 Sensitivitys hows that probability < 10– 11

Exchange-antisymmetric states of CO 2 For the CO 2 molecule states with odd values of J are missing because 16 O nuclei are Bosons. Mazzotti et al. PRL 86, 1919 (2001) looked for one: (0001)-(0000) R(25) calc at 2367. 265 cm-1 Sensitivitys hows that probability < 10– 11

Molecular Spectroscopy and Near-Symmetry P-violation CP-violation E(L) ≠ E(D) Life E( ) ≠ E( ) Matter TCP-violation or Spin stat violation Theoretical physics

Perfect Symmetry is OK: Symmetry is one idea by which man has tried to comprehend and create order, beauty and perfection. Hermann Weyl But Near-Symmetry is Irregularity is an essential feature of beauty, and that Richer: which is not slightly distorted is uninteresting. Charles P. Baudelaire

New ab initio calculations by D. Figgen and P. Schwertdfeger Barrier 1 (cm-1) SOHF 23000 Se. OHF 19000 Se. OCl. I 8500 Dip. Mom 2 (D) 2. 5 3. 3 2. 3 ΔEPV(S)3. (Hz) -0. 012 -0. 10 7. 8 1. One-component B 3 LYP using aug-cc-p. VTZ basis. 2. Dirac B 3 LYP, uncontracted dual family basis sets of about augmented triple to quadruple zeta quality. 3. Dirac B 3 LYP calculation for S-enantiomer.

The Standard Model of particle physics Particles: electron-neutrino, e, uq, dq All fermions Molecules muon-neutrino, muon, sq, cq tau-neutrino, tau, bq, tq [Aside: Proton is uud and neutron is udd ] Forces: electromagnetic, weak and strong. Force carriers: hν, W, Z, gluon (all bosons) Predicted: Higgs boson to give mass. 17 particles in all

Failures of Standard Model Cannot explain fields responsible for inflation; Matter-antimatter asymmetry-not enough CP violation; Invisible cold dark matter-not SM theory particles ; Gravity; The values of the masses of the quarks and leptons; The symmetrization principle. Various `extended’ supersymmetry theories devised and these theories give more CP-violation than the SM (they still maintain TCP symmetry). They also explain inflation and dark matter, but not gravity, the masses of the fundamental particles (or the symmetrization principle).

Stereoselective Photochemical Reactions Caused by Magnetochiral Dichroism • Wagnière and Meier: There is a difference in the absorption coefficients for enantiomers using unpolarized radiation in a magnetic field – a possible source for bio-homochirality. Experientia 39, 1090 (1983). • Rikken and Raupach: Nature 405, 932 (2000). Cr(III)tris-oxalato complex: D and L forms. Spontaneously dissociates and re-associates in solution. Light accelerates this dissociation. In a magnetic field one form absorbs more strongly; the more absorbing form dissociates more often but re-association forms equal amounts of each and we get an e. e. of less-absorbing form. If we change the direction of magnetic field we get an excess of the other enantiomer.

Stereoselective Chemistry on a Surface • Palache et al. 1962: Quartz. • Flores and Bonner 1974: Kaolin. • Wächtershäuser 1993: Iron pyrite • Hazen et al. 2001: Calcite • Zepik et al. 2002: Reaction at water surface “Polymerization on the Rocks: Theoretical Introduction” by Leslie Orgel in Origins of life 28, 227 (1998): “Impossible to synthesize long polymers of amino acids, nucleotides etc. , in homogeneous aqueous solution. We suggest pre-biotic synthesis on a mineral surface”

Enantiomeric Excess amplified by Crystallization • Landolt in Ber. d. deutsch. chem. Ges. 1896, p. 2410: One can precipitate crystals from aqueous sodium chlorate solution by adding alcohol. Equal amounts of minute l and d crystals are obtained. However, if add a little alcohol VERY SLOWLY get an e. e. In this latter case only a few seed crystals formed for which l/d is not exactly equal to one. • Kondepudi (1990) and Viedma (2005): Achieve same result by stirring a crystallizing solution to stop formation of many seed crystals. It is a competition between primary and secondary nucleation. If the experiment is repeated many times then the sum of all experiments will give a 50: 50 mixture of enantiomers.

Frank, Bonner and Zare, in `Chemistry for the 21 st Century, ’ Eds Keinan and Schecher, Wiley (2000) “Credible mechanisms have been identified for the extraterrestrial production and delivery to early Earth of organic molecules and amino acids containing a small e. e. The subsequent terrestrial sequestration of an initial e. e. and its amplification into dominance are processes for which biogenetically credible mechanisms exist. ”